Catalytic esterification of fatty acid with methanol, alkylation of 4-ethylphenol with benzyl alcohol as well as 2-methylfuran with cyclopentanone are of great significant for the production of biofuels. However, the in-situ produced water decreases the acidity of catalyst and induces side reaction, leading to an unsatisfactory catalytic activity and selectivity. Herein, a novel biochar-based hydrophobic benzenesulfonic acid is prepared for the first time by one-pot sulfonation method of biochar with 4-chlorobenzenesulfonic acid. It has a large specific surface area of 100-400 m(2)/g, a hydrophobicity with H2O contact angle higher than 110 degrees and a high concentration of sulfonic acid over 1.0 mmol/g. In the esterification reaction of fatty acid with methanol for synthesis of biodiesel, it shows a higher conversion of 96.0% than sulfonic acid resin amberlyst-15 (86.7%) and traditional sulfonated biochar-SO3H (28.0%). In the alkylation reaction of 4-ethylphenol with phenylmethanol/2-methylfuran with cyclopentanone for high-density bicyclic/monocyclic biofuel, its catalytic efficiency with target product yields are 69.4% and 70.5% respectively, which are also higher than that of amberlyst-15 (74.3%, 49.4%) and biochar-SO3H (14.7%, 13.0%). Furthermore, the catalyst is more stable than biochar-SO3H. The preparation of hydrophobic biochar-based sulfonic acid catalysts not only opens a new way for high-value utilization of biochar, but also provides a novel efficient catalyst in many acid-catalyzed transformation reactions that the product H2O causes deleterious effects.