Polychlorinated biphenyls (PCBs) are one group of persistent organic pollutants (POPs) that are of international concern because of global distribution, persistence, and toxicity. Removal of these compounds from the environment remains a very difficult challenge because the compounds are highly hydrophobic and have very low solubility in water. A 900 W domestic microwave oven, pyrex vessel reactor, pyrex tube connector and condensing system were used in this experiment. Radiation was discontinuous and ray powers were 540, 720 and 900 W. The PCBS were analyzed by GC-ECD. The application of microwave radiation and H2O2/TiO2 agents for the degradation of polychlorinated biphenyl contaminated oil was explored in this study. PCB – contaminated oil was treated in a pyrex reactor by microwave irradiation at 2450 MHz with the addition of H2O2/TiO2. A novel grain TiO2 (GT01) was used. The determination of PCB residues in oil by gas chromatography (GC) revealed that rates of PCB decomposition were highly dependent on microwave power, exposure time, ratio to solvent with transformer oil in 3:1, the optimal amount of GT01 (0.2 g) and 0.116 mol of H2O2 were used in the study. It was suggested that microwave irradiation with the assistance of H2O2/TiO2 might be a potential technology for the degradation of PCB – contaminated oil. The experiments show that MW irradiation, H2O2 oxidant and TiO2 catalyst lead to a degradation efficiency of PCBs only in the presence of ethanol. The results showed that the addition of ethanol significantly enhanced degradation efficiency of PCBs.