The Co-3(VO4)(2) multilayer nanoplates [Co-3(VO4)(2)-MNs] and Co-3(VO4)(2) ultrafine particle-comprised nanospheres [Co-3(VO4)(2)-UPNs] were prepared for the oxygen evolution reaction (OER). They are synthesized by a simple hydrothermal reaction using ethylenediaminetetraacetic acid and polyvinyl pyrrolidone as dispertants and pretectants. With the help of multi-walled carbon nanotubes (MWCNTs), the Co-3(VO4)(2)-MNs and Co-3(VO4)(2)-UPNs were immobilized respectivtly onto the surface of glassy carbon electrodes (GCEs). By comparison, the GCE-Co-3(VO4)(2)-MN/MWCNT exhibits higher performance of OER electrocatalysis and better stablity than the GCE-Co-3(VO4)(2)-UPN/MWCNT in the alkali electrolyte of 1 M KOH due to its higher surface roughness. The high surface free energy of Co-3(VO4)(2)-MNs is helpful for their immobilization on elelctrode surface, leading a better stability. The work shows that the noble metal-free electrocatalysts can lower the energy barrier and improve the energy efficiency for electrochemical water splitting to generate hydrogen. (C) 2015 Elsevier Ltd. All rights reserved.