A novel mesophilic anaerobic digestion process with detoxification-treated coconut shell pyroligneous was established, exhibiting an effective advantage in biogas production. The pyroligneous collected contained 166.2 g l(-1) acetic acid, indicating great potential for biogas production. Detoxification was an effective way of simultaneously enriching biodegradable ingredients and removing inhibitors (mainly as phenols and organic acids) for digestion process. The digestion process lasted 96 h and fermentation characteristics (chemical oxygen demand (COD) removal ratio, volatile fatty acid (VFA) consumptions, pH, total gas, methane yield, and phenol removal efficiency) were measured. The experiments successfully explored the optimum detoxification parameters, oxidized with 10 % H2O2 followed by overliming, and demonstrated 89.3 % COD removal, 91.4 % methane content, 0.305 L-CH4/g COD (removed) CH4 yield, and 88.81 % phenol removal ratio. This study provided clues to overcome the negative effects of inhibitors in pyroligneous on biogas production. The findings could contribute to significant process in detoxified pretreatment of pyroligneous and develop an economically feasible technology for treating pyroligneous after producing charcoal.