An X-ray fluorescence analyzer comprising: a sample stage having a mounting surface for mounting a sample; an X-ray source configured to irradiate the sample with the primary X-rays; a detector configured to detect fluorescent X-rays emitted from the sample irradiated with the primary X-rays; an X stage configured to move the sample stage in an X direction that is parallel to the mounting surface; a Y stage configured to move the sample stage in a Y direction that is parallel to the mounting surface and perpendicular to the X direction; a θ stage configured to have a rotation center (O') at the center of the mounting surface and to rotate the sample stage around a rotation axis perpendicular to the mounting surface; a shielding container configured to accommodate the sample stage, the X-ray source, the detector, the X stage, the Y stage, and the θ stage; an imaging unit; a display unit configured to display an image captured by the imaging unit; and an image processing unit, characterized by that the X-ray source is disposed immediately above an irradiation position of the sample and that the x-ray fluorescence analyzer further comprises a control unit configured to control the analyzer such that the irradiation position with the primary X-rays is set at an offset position from a movement center of the X stage and the Y stage, and an irradiation area that is irradiatable with the primary X-rays is set to a selected segmented area, in which the irradiation position is disposed, from among segmented areas that are defined by segmenting the surface of the sample into four parts with a virtual segment line in the X direction and a virtual segment line in the Y direction passing through the movement center when the X stage and the Y stage are moved in a state in which the θ stage is not moved, wherein the θ stage is configured to switch the selected segmented area as the irradiation area into any one of the segmented areas by rotating the sample stage by every 90 degrees, wherein the imaging unit is configured to capture an image of the segmented area selected as the irradiation area; wherein the image processing unit is configured to arrange images of the four segmented areas captured by the imaging unit while the four segmented areas are switched by the θ stage, and generate a combined image of an entire surface of the sample stage to be displayed on the display unit, wherein the image processing unit is further configured to generate the combined image by rotating the images of the four segmented areas in a reverse direction by the same degree of rotation as the rotation of the θ stage when each of the images of the four segmented areas is set as the irradiation area, and wherein the control unit is configured to designate the irradiation area on the combined image or is designated based on the coordinates on the sample stage. a sample stage having a mounting surface for mounting a sample; an X-ray source configured to irradiate the sample with the primary X-rays; a detector configured to detect fluorescent X-rays emitted from the sample irradiated with the primary X-rays; an X stage configured to move the sample stage in an X direction that is parallel to the mounting surface; a Y stage configured to move the sample stage in a Y direction that is parallel to the mounting surface and perpendicular to the X direction; a θ stage configured to have a rotation center (O') at the center of the mounting surface and to rotate the sample stage around a rotation axis perpendicular to the mounting surface; a shielding container configured to accommodate the sample stage, the X-ray source, the detector, the X stage, the Y stage, and the θ stage; an imaging unit; a display unit configured to display an image captured by the imaging unit; and an image processing unit, characterized by that the X-ray source is disposed immediately above an irradiation position of the sample and that the x-ray fluorescence analyzer further comprises a control unit configured to control the analyzer such that the irradiation position with the primary X-rays is set at an offset position from a movement center of the X stage and the Y stage, and an irradiation area that is irradiatable with the primary X-rays is set to a selected segmented area, in which the irradiation position is disposed, from among segmented areas that are defined by segmenting the surface of the sample into four parts with a virtual segment line in the X direction and a virtual segment line in the Y direction passing through the movement center when the X stage and the Y stage are moved in a state in which the θ stage is not moved, wherein the θ stage is configured to switch the selected segmented area as the irradiation area into any one of the segmented areas by rotating the sample stage by every 90 degrees, wherein the imaging unit is configured to capture an image of the segmented area selected as the irradiation area; wherein the image processing unit is configured to arrange images of the four segmented areas captured by the imaging unit while the four segmented areas are switched by the θ stage, and generate a combined image of an entire surface of the sample stage to be displayed on the display unit, wherein the image processing unit is further configured to generate the combined image by rotating the images of the four segmented areas in a reverse direction by the same degree of rotation as the rotation of the θ stage when each of the images of the four segmented areas is set as the irradiation area, and wherein the control unit is configured to designate the irradiation area on the combined image or is designated based on the coordinates on the sample stage.