Photocatalysis has been studied and considered as a green and practical approach in addressing environmental pollution. However, factors that affect photocatalytic performance have not been systematically studied. In this work, we have presented a comprehensive roadmap for characterizing, interpreting, and reporting semiconductors’ electrical and optical properties through routinely used techniques such as diffuse reflectance spectroscopy, electrochemical techniques (Mott–Schottky plots), photoluminescence, X-ray photoelectron spectroscopy, and ultraviolet photoelectron spectroscopy in the context of photocatalysis. Having precisely studied the band structure of three representative photocatalysts, we have presented and highlighted the essential information and details, which are critical and beneficial for studies of (1) band alignments, (2) redox potentials, and (3) defects. Further works with a comprehensive understanding of the band structure are desirable and hold great promise.