A new zinc phosphite cluster, Zn 2 (4,4′-dmbpy) 2 (H 2 PO 3 ) 4 1, and a new chainlike zinc phosphate, Zn 2 (5,5′-dmbpy) 2 (HPO 4 )(H 2 PO 4 ) 2 2, have been synthesized under hydrothermal conditions (4,4′-dmbpy=4,4′-dimethyl-2,2′-dipyridy, 5,5′-dmbpy=5,5′-dimethyl-2,2′-dipyridy). Compound 1 is a molecular zinc phosphite constructed from ZnO 3 N 2 trigonal bipyramids, H 2 PO 3 pseudo-pyramids and 4,4′-dmbpy ligands. Compound 2 possesses a 1D chainlike framework constructed from ZnO 3 N 2 trigonal bipyramids, HPO 4 tetrahedra, H 2 PO 4 tetrahedra and 5,5′-dmbpy ligands. Both compounds 1 and 2 exhibit intensive photoluminescence originated from the intraligand π–π* transitions. Crystal data: 1, monoclinic, P2 1 /n, a=8.0310(7)Å, b=20.2301(5)Å, c=10.8424(2)Å, β=110.857(3)°, V=1646.11(15)Å3, Z=2, R1=0.0297, wR1=0.0801; 2, triclinic, P-1, a=11.6875(8)Å, b=12.3498(7)Å, c=13.1759(8)Å, α=64.995(9)°, β=65.952(9)°, γ=65.296(8)°, V=1502.99(16)Å3, Z=2, R1=0.0418, wR1=0.1010.