Tetra-carboxylic acid based 3D porous MOFs 1 and 2, named {[Co-2.5(L)]center dot 5H(2)O](n) and 0.5 {[CuN]center dot 2H(2)Ol n = 4,4'-di(ethoxy)biphenyl-3,3',5,5'-tetra-(phenyl-4-carboxylic acid)), bearing metal clusters have been facilely constructed by hydrothermal synthesis. Structural studies indicate that 1 presents a 3-nodal (4, 4, 8)-connected topology with the point notation of {4(4).6(2)}2{4 (8).6(7).8(13)}, while 2 shows a uninodal (4, 4)-connected network with point symbol of {4(4).6(2)}. The pristine MOFs are directly utilized for electrocatalysis and poor HER activities are obtained in alkaline solution, which promote the further design and fabrication of a mixed-metal Co/Cu-MOF (3). As expected, 3 shows significantly improved performances for HER with overpotential of 391 mV (10 mA cm(-2) current density), low Tafel slope of 94 mV dec(-1) and long-term operation stability (14 h). More importantly, the direct utilization of 3 for accelerating OER also presents a fascinating performance in overpotential at 10 mA cm(-2) current and durability. The above electrocatalytic performance of pristine 3 can be ascribed to the result of hybridizing strategy for constructing MOFs under hydrothermal procedure, which may favorably produces synergistic effect and more open metal sites. This work provides in-depth understanding of hybrid pristine MOFs for electrocatalysis. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.