Developing high-performance artificial enzyme materials with practical applications in efficient catalytic hydrolysis detoxification of organophosphate (OP) nerve agents remains a formidable challenge. Herein, UiO-66-NH2-stabilized Pickering high internal phase molecularly imprinted polymer systems (MOFs@PHIPMIPs) were developed using OPs as template molecules. Thus, UiO-66-NH2-doped high-internal-phase MIP composites were obtained, which integrate MIPs and MOFs successfully, showing remarkable catalytic hydrolysis activity towards OPs. In addition, by introducing methyl methacrylate (MMA) during copolymerization, the MOFs@PHIPMIPs would effectively acquire pH buffering properties. The multi-porous composite catalysis system exhibits an exceptionally high detoxification efficiency towards dimethyl-4-nitrophenyl phosphate (DMNP) in pure water (k(obs) = 0.9162 min(-1), t(1/2) = 0.76 min). This work presents a new strategy for the preparation of artificial phosphatase materials with high-performance catalytic detoxification of OPs with great application prospects.