An X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy alignment system comprising: a. a vacuum chamber ; b. a sample stage mounted within the vacuum chamber; c. a Raman spectrometer having a Raman laser for providing a Raman laser beam; d. a Raman laser transfer optical assembly mounted within the vacuum chamber and configured to focus the Raman laser beam from the Raman spectrometer on a selected area on the sample stage ; e. a video camera mounted outside the vacuum chamber and configured to provide images of the sample stage; and f. an X-ray source mounted within the vacuum chamber and configured to direct X-rays toward the same selected area of the sample stage ; characterised by g. an X-ray alignment indicator mounted on the sample stage that provides a visual indication of X-ray location viewable by the video camera on the sample stage in response to X-rays directed toward the sample stage ; h. an X-ray location for the X-rays and a laser beam location for the Raman laser beam on the sample stage configured to be substantially the same size and each less than about 20 microns in diameter; and i. a position of the Raman laser beam configured to be adjustable in X and Y directions of an X-Y plane , such that the laser beam location can be aligned with the X-ray location on the sample stage , wherein the adjustable position of the Raman laser beam is provided by the Raman spectrometer being mounted on a base plate that is mounted on the vacuum chamber , the base plate being adjustable in the X and Y directions of the X-Y plane, or by at least two kinematic mirrors located outside of the Raman spectrometer . a. a vacuum chamber ; b. a sample stage mounted within the vacuum chamber; c. a Raman spectrometer having a Raman laser for providing a Raman laser beam; d. a Raman laser transfer optical assembly mounted within the vacuum chamber and configured to focus the Raman laser beam from the Raman spectrometer on a selected area on the sample stage ; e. a video camera mounted outside the vacuum chamber and configured to provide images of the sample stage; and f. an X-ray source mounted within the vacuum chamber and configured to direct X-rays toward the same selected area of the sample stage ; characterised by g. an X-ray alignment indicator mounted on the sample stage that provides a visual indication of X-ray location viewable by the video camera on the sample stage in response to X-rays directed toward the sample stage ; h. an X-ray location for the X-rays and a laser beam location for the Raman laser beam on the sample stage configured to be substantially the same size and each less than about 20 microns in diameter; and i. a position of the Raman laser beam configured to be adjustable in X and Y directions of an X-Y plane , such that the laser beam location can be aligned with the X-ray location on the sample stage , wherein the adjustable position of the Raman laser beam is provided by the Raman spectrometer being mounted on a base plate that is mounted on the vacuum chamber , the base plate being adjustable in the X and Y directions of the X-Y plane, or by at least two kinematic mirrors located outside of the Raman spectrometer . <EOS>