A 3D 4-coordinated self-catenated metal–organic framework {[Co(bibp)(1,4-chdc)]•2H2O}n (1) (bibp = 4,4´-bis(1-imidazolyl)biphenyl, 1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid) has been synthesized under hydrothermal reaction and its structure has been determined. This framework buries an unprecedented 4-coordinated self-catenated net that can be represented as an array honeycomb-like units catenated in an inclined mode, with the highest topological density among the 4-coordinated nets that occurred in crystal structures. Additionally, the thermogravimetric, photo-catalytic and electrochemical behaviors have been investigated.