A new two-dimensional inorganic–organic hybrid solid, formulated as Cd₁₇S₄(SPh)₂₅B(im)₄ (SPh = benzenethiolate, im = imidazolate), has been synthesized under solvothermal conditions. The structure features a 6³ network with 17-nuclear cadmium clusters linked by B(im)₄⁻ ligands. The compound is a semiconductor with the band gap of 2.66 eV and displays a green luminescence upon excitation at 390 nm.