Two coordination polymers {[Cu 4 (OH) 2 (btrb) 2 (btc) 2 ]·4H 2 O} n (1) and {[Cd 2 (btrb)(adc) 2 (H 2 O)]·H 2 O} n (2) were synthesized with hydrothermal method and characterized (btrb=1,4-bis(1,2,4-triazol-4-ylmethyl)benzene, btc=1,3,5-benzenetricarboxylate, adc=1,3-adamantanedicarboxylate). 1 shows an unusual (3,10)-connected two-dimensional metal–organic framework based on the tetranuclear copper(II) cluster [Cu 4 (μ 3 -OH) 2 ]. 2 is an interesting three-dimensional network based on the one-dimensional metal–organic nanotube. 1 shows good photocatalytic activity for the degradation of methyl blue (MB). The luminescence of 2 was investigated.