The dinuclear complex [Cu 2 (dpbp) 2 (NCMe) 4 ][BF 4 ] 2 (1) has been prepared by treating [Cu(NCMe) 4 ][BF 4 ] with 4,4′-bis(diphenylphosphino)biphenylene (abbreviated as dpbp). Reactions of 1 with 2,2′-bipyridine and 1,1′-bis(diphenylphosphino)ferrocene (abbreviated as dppf) afford [Cu 2 (dpbp) 2 (2,2′-bipy) 2 ][BF 4 ] 2 (2) and [Cu 2 (dpbp)(dppf) 2 ][BF 4 ] 2 (3), respectively. In contrast, compound 1 reacts with tetra(2-pyridyl)ethyl-1,4-diaminobutane (abbreviated as tpyda) to produce the polymeric complex {[Cu 2 (dpbp)(tpyda)][BF 4 ] 2 } n (4). Compounds 1–4 are photoluminescent with the emission band (λ max ) in the range 510–554nm. The crystal structures of 1 and 4 have been determined by an X-ray diffraction study.