Electrocatalytic water splitting catalyst plays an important role in clean energy conversion system. Herein, we use [CH3NH3][ZnxCo1-x(HCOO)(3)] as precursors to prepare hollow ZnxCo1-xSe2 microcubes by a simple solvothermal strategy. Particularly, the synthesized hollow Zn0.1Co0.9Se2 microcube presents the best electrocatalytic performance, with a current density of 10 mA cm(-2) at overpotential of only 196 mV for HER in acid and 308 mV for OER in alkaline solution, respectively. The hollow porous structure and a handful of zinc doping contribute to enhancing electrocatalytic performance. The former is conducive to expose more active sites, while the latter not only can improve the conductivity of the electro-catalyst, but also enhance the hydrogen adsorption capacity of the material. The synthesis method is simple, low toxicity and has no high temperature carbonization process, which provides a good prospect for the synthesis of non-precious metal bifunctional electro-catalysts with hollow structure. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.