A current collector-catalyst monolithic porous nanofiber network electrode suitable for use in a Li-air battery, the current collector-catalyst monolithic porous nanofiber network electrode comprising: a porous nanofiber network having a fabric-like structure formed by a plurality of non-electrically conductive nanofibers and a void space formed between the plurality of nanofibers, wherein the current collector-catalyst monolithic porous nanofiber network electrode has a core-shell structure including the porous nanofiber network as a center layer (core) and a shell coated on a surface of the plurality of nanofibers comprising a single catalyst layer, wherein the shell of the core-shell structure is uniformly and continuously coated on the surface of the individual nanofibers, comprises an electrically conductive layer, and the single catalyst layer is non-electrically conductive and in the form of a nanosheet or a nanofilm, wherein the porous nanofiber network includes a thermally stable polyimide nanofiber as the center layer suitable for a stable subsequent process or treatment including a subsequent heat treatment or a high-temperature deposition process at a temperature of 200°C or higher, wherein the electrically conductive layer and non-electrically conductive single catalyst layer are continuously layered and formed on a surface of the plurality of nanofibers as a first coating layer and a second coating layer, respectively, to form the shell, wherein the electrically conductive layer has a thickness range of 20 to 500 nm, wherein the catalyst layer includes a non-electrically conductive catalyst layer having a thickness range of 5 to 20 nm, and wherein the catalyst layer includes a single material or a mixture of two or more composite materials of a two-component system metal oxide including at least one of cobalt oxide (Co 3 O 4), manganese oxide (MnO 2), or nickel oxide (NiO) and a three-component system metal oxide including at least one of lanthanum-manganese oxide (LaMnO 3), lanthanum-cobalt oxide (LaCoO 3), or lanthanum-iron oxide (LaFeO 3). a porous nanofiber network having a fabric-like structure formed by a plurality of non-electrically conductive nanofibers and a void space formed between the plurality of nanofibers, wherein the current collector-catalyst monolithic porous nanofiber network electrode has a core-shell structure including the porous nanofiber network as a center layer (core) and a shell coated on a surface of the plurality of nanofibers comprising a single catalyst layer, wherein the shell of the core-shell structure is uniformly and continuously coated on the surface of the individual nanofibers, comprises an electrically conductive layer, and the single catalyst layer is non-electrically conductive and in the form of a nanosheet or a nanofilm, wherein the porous nanofiber network includes a thermally stable polyimide nanofiber as the center layer suitable for a stable subsequent process or treatment including a subsequent heat treatment or a high-temperature deposition process at a temperature of 200°C or higher, wherein the electrically conductive layer and non-electrically conductive single catalyst layer are continuously layered and formed on a surface of the plurality of nanofibers as a first coating layer and a second coating layer, respectively, to form the shell, wherein the electrically conductive layer has a thickness range of 20 to 500 nm, wherein the catalyst layer includes a non-electrically conductive catalyst layer having a thickness range of 5 to 20 nm, and wherein the catalyst layer includes a single material or a mixture of two or more composite materials of a two-component system metal oxide including at least one of cobalt oxide (Co 3 O 4), manganese oxide (MnO 2), or nickel oxide (NiO) and a three-component system metal oxide including at least one of lanthanum-manganese oxide (LaMnO 3), lanthanum-cobalt oxide (LaCoO 3), or lanthanum-iron oxide (LaFeO 3).