Biological treatments focused on stabilizing and detoxifying olive mill wastewater facilitate agronomic reuse for irrigation and fertilization. Anaerobic digestion is particularly attractive in view of energy recovery, but is severely hampered by the microbial toxicity of olive mill wastewater. In this work, the addition of biochar to the digestion mixture was studied to improve the stability and efficiency of the anaerobic process. Kinetics and yields of biogas production were evaluated in batch digestion tests with biochar concentrations ranging from 0 to 45 g L−1. The addition of biochar reduced sensibly the lag phase for methanogenesis and increased the maximum rate of biogas generation. Final yields of hydrogen and methane were not affected. Upon addition of biochar, soluble COD removal increased from 66% up to 84%, and phenolics removal increased from 50% up to 95%. Digestate phytotoxicity, as measured by seed germination tests, was reduced compared to raw wastewater. Addition of biochar further reduced phytotoxicity and, furthermore, a stimulatory effect was observed for a twenty-fold dilution. In conclusion, biochar addition enhances the anaerobic digestion of olive mill wastewaters by effectively reducing methanogenesis inhibition and digestate phytotoxicity, thus improving energy and biomass recovery.