Microstructures and electrochemical characteristics of La0.7Ce0.3Ni4.2Mn0.9-xCu0.37(V0.81Fe0.19)(x) hydrogen storage alloys were investigated. X-ray diffraction and scanning electron microscope results indicate that La0.7Ce0.3Ni4.2Mn0.9Cu0.37 alloy is single LaNi5 phase, and the alloys containing V0.81Fe0.19 consist of LaNi5 matrix phase and V-Mn-Ni secondary phase, and the abundance of secondary phase increases with increasing x value. The activation property of the alloy electrodes is improved by increasing V0.91Fe0.19 content. Maximum discharge capacity of the alloy electrodes changes a little with increasing x value. HRD1200 first increases from 60.4% (x=0) to 70.8% (x=0.10), and then decreases to 56.6% (x=0.20). Cycling stability decreases with increasing x from 0 to 0.20. The adequate substitution of Mn by V0.81Fe0.19 can improve overall electrochemical performances of Co-free high-Mn AB(5) alloy. (C) 2013 Elsevier Ltd. All rights reserved.