The Macroporous Nanocrystalline TiO2 Thin Film Was Prepared by Dipping-Coating Method. Polystyrene (PS) Microspheres Template Was Used as Pore-Forming Assistant and TiO2 Sol Was Used as Precursor. the Photoelectric Characteristics of the Samples Were Studied Using Surface Photovoltage (SPV) and Photoacoustic (PA) Techniques. the Presence of a Small Amount of Residual Template Damages the Integrity of the Porous TiO2 Film with Inverse Opal Structure, and TiO2 May Be Restricted in Certain Application Fields as Photonic Crystals. a Small Amount of Residual Template Changes the Surface Photovoltaic Properties of the Porous TiO2 Film, Resulting Mainly in the Broadened Scope and the Increased Intensity of SPV Response.