Advanced oxidation processes (AOPs) are potential technologies for the treatment of wastewaters containing non-easily removable organic compounds. Isopropyl alcohol (IPA) is one of the groups with high toxicity and low biodegradability and is always interested by researchers. In this study, Chemical Vapor Deposition (CVD) was used to immobilize TiO2 photocatalyst on the titanium substrate plate and extra applied electric potential on the working electrode (anode) combined with a 365 nm UV lamp for irradiating the IPA wastewater to conduct a photoelectrocatalytic reaction. The experimental results showed, during the photoelectrocatalytic reaction, the extra applied electric potential could inhibit the recombination of the electron-hole pair and raise the overall removal efficiency. However, when the potential was more than 0.5 V, it would reduce the photoelectrocatalytic effect because of the recombination of electrons and holes. Moreover, adding different electrolyte solutions enhanced the different degree of effects of IPA removal. Among the electrolyte solutions added, sodium sulfate improved the photoelectrocatalytic effect most significantly.