Studies on synthesis, structures, and photophysics have been carried out for a series of luminescent copper(I) halide complexes with the chelating ligand, 1,2-bis[diphenylphosphino]benzene (dppb). The complexes studied are halogen-bridged dinuclear complexes, [Cu(mu-X)dppb](2) (X = I (1), Br (2), Cl (3)), and a mononuclear complex, CuI(dppb)(PPh3) (4). These complexes in the solid state exhibit intense blue-green photoluminescence with microsecond lifetimes (emission peaks, lambda(max) = 492-533 nm; quantum yields, Phi = 0.6-0.8; and lifetimes, tau = 4.0-10.4 mu s) at 298 K. In 2-methyltetrahydrofuran (2mTHF) solutions at 298 K, only 1 and 4 show weaker emission (Phi = 0.009) with shorter lifetimes (tau = 0.35 and 0.23 mu s) and red-shifted spectra (lambda(max) = 543 and 546 nm). The emission in the solid state originates from the (M + X)LCT excited state with a distorted-tetrahedral conformation, in which emissive excited states, (1)(M + X)LCT and (3)(M + X)LCT, are in equilibrium with an energy difference of similar to 2 kcal/mol. On the other hand, the complexes in the 2mTHF solutions emit from the MLCT excited state with an energetically favorable flattened conformation in the temperature range of 298-130 K. The flattened geometry with equilibrated (MLCT)-M-1 and (MLCT)-M-3 states has a nonradiative rate at least 2 orders of magnitude larger than that of the distorted-tetrahedral geometry, leading to a much smaller emission quantum yield (Phi = 0.009) at 298 K. Since the flattening motion is markedly suppressed below 130 K, the emission observed in 2mTHF below 130 K is considered to occur principally from the (M + X)LCT state with a distorted-tetrahedral geometry. To interpret the photophysics of V 1 and 4 in both the solid and solution states, we have proposed the "2-conformations with 2-spin-states model (2C x 2S model)". The electroluminescence device using (1) as a green emissive dopant showed a moderate EL efficiency; luminous efficiency = 10.4 cd/A, power efficiency = 4.2 lm/W at 93 cd/m(2), and maximum external quantum efficiency = 4.8%.