The title complex [(phen)2Cu(Htcb)Cu(phen)2]H3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.