Searching for non-precious metal anode catalysts with high catalytic activity and capable of inhibiting hydrolysis side reactions is very important for direct borohydride fuel cell (DBFC). In this work, the as-cast AB(5) alloy powders are firstly mixed with CNTs in a ratio of 1:9. Then the mixture of AB(5) alloy and CNTs is ball milled in different milling time. Finally, the CNTs/AB(5) composite alloys are obtained. Not only the catalytic properties of the CNTs/AB(5) composite alloys used as anode catalysts in DBFC, but also the electrochemical properties of the alloys have been investigated in detail. The research results indicate that, as the ball milling time is extended, the electrochemical properties and catalytic properties on BH4- of the CNTs/AB(5) composite alloys become better first and then worsen. The CNTs/AB(5) alloy milled 2 h exhibits the best electrochemical properties and catalytic properties. Furthermore, we predict that the electrochemical properties of the composite alloy are positively correlated with the catalytic properties as anode catalyst for DBFC. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.