Microbial degradation is an elimination method for removal of organic contaminants from soil and water. However, the main factor limiting its practical application is high bacterial sensitivity to environmental factors such as pH, toxicity, and mass transfer. In this study, biochar was produced pyrolytically from peanut shells at 350 °C, 550 °C, and 750 °C (referred to as BC350, BC550, and BC750, respectively) and their promotion on phenol biodegradation in wastewater by the bacterium Pseudomonas citronellolis was investigated. Higher initial phenol concentration (>400 mg L) showed obvious inhibition on biodegradation with the removal efficiencies being less than 46%, and even the bacterium failed to survive at the phenol concentrations of higher than 1000 mg L. With biochar incorporated, the removal efficiencies of phenol increased from below 46% to up to 99% at the initial concentrations of 400-1200 mg L. Immobilization of strains in biochar by calcium alginate further increased the microbial tolerance to high concentrations of phenol (i.e., 63% removal at 1200 mg L). Scanning electron microscopy demonstrated that biochar acted as shelter to support the bacterium to struggle with extreme conditions. The initial adsorption of phenol by biochar alleviated the initial toxicity of phenol to bacterium and the subsequent gradual desorption controlled the bioavailability of phenol. In this regard, BC350 showed a comparable sorption capacity with BC550 and BC750, while a higher desorption potential than them, thus balanced better the toxicity and bioavailability of phenol to microbes. Alkalinity of BC550 and BC750 played important roles in rescuing the microbes from being damaged by pH shock via neutralizing the fast generation of acidic intermediates. The extractable organic substances in BC350 could be consumed by bacterium as substrates, which was confirmed by incubating the strains in water-extractable solution. Results of this study indicate that incorporation of microbes with biochar could promote the biodegradation of high concentration organic wastewater.