Based on the ligand 1,4-bis(2-(diphenylphophino)benzylideneamino)benzene (pbb), two complexes, [Cu₂(pbb)(2,2′-bipyridine)₂](BF₄)₂ (1) and [Cu₂(pbb)(phen)₂](BF₄)₂ (2), have been prepared and characterised by IR, ¹H NMR, ³¹P NMR, ¹⁹F NMR, and ¹¹B NMR spectroscopy and X-ray crystal structure analysis. Structural analysis reveals that complexes 1 and 2 contain 1D infinite chains and 2D supramolecular networks constructed by C–H···π and π···π interactions, and an ordered-layer-lattice of BF₄^– is located between these 2D networks. The results show that C–H···π and π···π interactions play an important role in the formation of 2D supramolecular networks. The UV-vis absorption peaks of complexes 1 and 2 display intraligand charge transfer and metal to ligand charge transfer (MLCT) absorption. Complexes 1 and 2 display efficient luminescent emission assigned to MLCT excited states, and the maximum emissions of these complexes in acetonitrile solution are different from those of the solid-state samples. In addition, complexes 1 and 2 have been exploited as sensitisers in dye-sensitised solar cells, and efficiencies are also observed.