A new 3D organic-inorganic hybrid solid ［Cu4(SCN)4(bpp)2］n (1) was obtained via the self-assembly of inorganic ladder-like chains ［Cu(SCN)］n with the flexible organic ligands 1,3-di(4-pyridyl)propane (bpp) under solvothermal conditions. It is noted that the bpp ligands show two kinds of conformations (trans-gauche or trans-trans) in the asymmetric unit, which linked by similar staircase-like ［Cu(SCN)］n chains to form crystallographically distinct ［Cu2(SCN)2(bpp)］n layers A and B. Furthermore, two different layers are packed in an offset ABB′A′ pattern to generate unique 3D structure. Compound 1 was further characterized by infrared spectroscopy (FT-IR), powder diffraction (PXRD), thermal analysis, solid state diffuse reflectance spectroscopy (UV-Vis) and photoluminescent studies. The solid UV-Vis diffuse-reflectance spectroscopy shows strong absorption spectra in ultraviolet region, and a wide-gap semiconductor with band gap of 3.20 eV. Compound 1 shows different photocatalytic activities for neutral red (NR), methyl orange (MO), azure I (AI), methylene blue (MB) and brilliant blue (ED) degradation under UV-light irradiation, which could be related to the slight charge and size difference of organic dyes. Compound 1 shows strong green photoluminescence at room temperatures with emission peaks at about 525 nm, which may be associated with a ligand-centered excited state with a possible involvement of metal-to-ligand or ligand-to-ligand charge transfer.