Transparent conducting films are an important class of materials for optoelectronics. Other than the transmission in the wavelength of visible light and the conductivity, the energy band alignments of transparent conducting films to other materials in the optoelectronic devices, such as solar cells, are also keys to the performance of the devices. Therefore, the analysis of the energy levels of these materials is crucial in the development of these materials. In this article, we will review the materials for the transparent conducting films and the principles of photoemission spectroscopy. The application of photoemission spectroscopy to energy band alignment measurement and the surface analysis will also be discussed.