The core-shell structured polypyrrole/polyaniline (PPy@PANI) were synthesized by in-situ polymerization method and were used as the conductive medium to enhance methane production from the anaerobic wastewater treatment. It was found that the PPy@PANI has a good performance on methane production from the anaerobic wastewater treatment, and it composites can improve the methane production rate and yield by 70.2% and 28.3% in the initial 4 h compared with the control group. A high methane production rate was achieved when the dosage of PPy@PANI was 0.6 g/L, which suggested that 0.6 g/L was the optimal dosage. Finally, the mechanisms involved in the improved methane production rate by the PPy@PANI were disclosed. The PPy@PANI can enrich the functional microorganisms to enhance both the degradation of organics and the electron transfer, which contributed to the improved methane production rate from the anaerobic wastewater treatment.