ZnAl-layered double hydroxide with silver additive (Ag/ZnAl-LDH) composites with a plate-like structure were fabricated by a facile silver mirror reaction and their electrochemical performance had been evaluated as anode materials for Ni-Zn secondary batteries. Structure and morphology analysis showed that silver additive was dispersed on the surface of ZnAl-LDH nanosheets. Electrochemical performances were evaluated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge–discharge tests. The results of charge–discharge tests showed that silver additive could improve the cycle performance and discharge capability of ZnAl-LDH as anode materials for Ni-Zn secondary batteries. Further analysis (such as CV and EIS) indicated that the improved electrochemical performance caused by silver additive was associated with the enhancement of electrical conductivity of the material and the lower polarization of the cell.