Polyvinyl alcohol (PVA) is the main pollutant in printing and dyeing wastewaters. This pollutant exhibits great demand, poor biodegradability and refractory degradation. In this study, PVA wastewater treatment experiments were conducted in a stably operating baffled anaerobic bioreactor (ABR) by using simulated PVA wastewater. The PVA degradation pathway and mechanism of the mixed dominant PVA-degrading bacterial strains were identified through the analysis of their degradation products. From the results, we inferred that PVA was degraded in a stepwise process under the synergistic action of different extracellular and intracellular enzymes produced by the mixed dominant PVA-degrading bacterial strains. In this process, PVA was first degraded into ketones, fatty acids and alcohols. It was then regenerated into acetic acid, hydrogen and carbon dioxide. Finally, these substances could be further utilized by methanogens. PVA was thus degraded completely. This study may serve as a reference for future works on the degradation of PVA in the ecological environment. It may also guide the sustainable development of PVA.