Development of robust and cheap catalyst for fast hydrogen evolution from ammonia borane (AB) aqueous solution is an interesting and important topic in the field of hydrogen energy. Herein, a novel non-precious Co3xCu3-3x(PO4)(2) catalyst possessing high reactivity in AB hydrolysis has been developed for the first time. By tuning the molar ratio of Co and Cu, a series of Co3xCu3-3x(PO4)(2) with different x were synthesized and the catalytic behavior in AB hydrolysis was examined. At the optimal x of 0.8, an ultrahigh turnover frequency of 72.6 min(-1) was achieved. Additionally, the synergistic effect between Cu-3(PO4)(2) and Co-3(PO4)(2) was experimentally confirmed, and the reaction kinetics of AB hydrolysis catalyzed by Co2.4Cu0.6(PO4)(2) were investigated. This work provides a simple route and some new insights for the fabrication of a cheap P-containing catalyst with robust catalytic performance. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.