Two copper(I) coordination polymers, {[Cu2(pmb)(4,4′-bipyridine)(PPh3)2] (BF4)2(CH3CN)2}n (1) and {[Cu2(pmb)(bpe)(PPh3)2](BF4)2(CH3CN)(H2O)}n (2) (pmb=N,N′-bis(pyridin-2-ylmethylene)benzene-1,4-diamine, bpe=1,2-bis(4-pyridyl)ethylene), PPh3=triphenylphosphine), have been prepared and characterized by IR, 1H NMR, 13C NMR, 31P NMR, 19F NMR, 11B NMR, TG and X-ray crystal structure analysis. The structural analysis shows that each 1D zig-zag chain in 1 interacts with neighbouring acetonitrile molecules, interestingly, which results in the formation of CN⋯π interactions around this chain. For 2, 1D helical tube is formed by directly linking horse-shoe shaped collar with a 32-membered split ring, while C–H⋯π interaction results in the stacking of 1D helical tube into a 3D network. In complexes 1 and 2, the solid-state UV–Vis absorption peaks show the existence of MLCT absorption. Furthermore, complexes 1 and 2 indicate efficient luminescent emission peaks near 450nm attributed to MLCT excited states, and the emission decay lifetimes of complexes 1 and 2 are 28.33μs and 29.99μs, showing strong solid-state photoluminescence at room temperature. In addition, TG-DTA reveals that the heat stability of these complexes is 1>2.