Biochars were produced from pig manure to elucidate the influence of biochars with high ash contents on the fate of pesticides. Adsorption and catalytic hydrolysis of carbaryl and atrazine on original biochars and deashed biochars were investigated. The two pesticides were substantially adsorbed by the biochars, with organic carbon normalized sorption coefficient (Koc) values of 102.65–103.66 L/kg for carbaryl and 101.90–103.57 L/kg for atrazine at Ce of 0.5 mg/L. Hydrophobic effect alone could not explain the sorption, and several other processes including pore-filling and π–π electron donor–acceptor interactions were involved in pesticide adsorption. Adsorption increased greatly on the deashed biochar, indicating that some organic sorption sites in the original biochars were blocked or difficult to access due to their interactions with inorganic moiety. The pesticides were found to hydrolyze faster in the presence of biochars, and in the presence of biochar pyrolyzed at 700 °C, carbaryl and atrazine were decomposed by 71.8% and 27.9% in 12 h, respectively. The elevated solution pH was the main reason for the enhanced hydrolysis; however both the mineral surface and dissolved metal ions released from the biochars were confirmed to catalyze the hydrolysis.