Old Corrugated Container (OCC) pulping wastewater has a complex organic composition and high levels of biotoxicity. The presence of dissolved and colloidal substances (DCSs) is a major limiting factor for pulp and paper companies to achieve closed-water recycling. In order to solve this problem, the coupled ozone-catalyzed oxidation and biodegradation (OCB) method was used to treat OCC pulping wastewater in this study. A polyurethane sponge was used as the basic skeleton, loaded with nano TiO2 and microorganisms, respectively, and then put into a reactor. After an 8-min ozone-catalyzed oxidation reaction, a 10-h biological reaction was carried out. The process was effective in removing organic pollutants such as COD and BOD5 from OCC paper whitewater. The removal rates of COD and BOD5 were 81.5% and 85.1%, respectively. By using the polyurethane sponge to construct a microenvironment suitable for microbial growth and metabolism, this study successfully applied and optimized engineered bacteria—white rut fungi (WRF)—in the system to achieve practical degradation of OCC pulping wastewater. Meanwhile, the biocompatibility of different microbial communities on the polyurethane sponge was analyzed by examining the degradation performance of OCC pulping wastewater. The structure of microbial communities loaded on the polyurethane sponge was analyzed to understand the degradation mechanism and microbial reaction behavior. White-rot fungi (Phanerochaete) contributed more to the degradation of OCC wastewater, and new strains adapted to OCC wastewater degradation were generated.