Dicapped triangular copper(I)−dppm complexes Cu3(dppm)3(μ3-X)2+ (X = Cl, Br, and I) and monocapped Cu3(dppm)3(μ3-OH)2+ have been prepared by treating the dimeric Cu2(dppm)2(CH3CN)4(ClO4)2 or Cu2(dppm)2(dmcn)3(BF4)2 (dmcn = dimethylcyanamide) complexes with the corresponding bridging ligand X-. The trimeric complexes Cu3(dppm)3(μ3-OH)(BF4)2 and Cu3(dppm)3(μ3-Cl)2Cl can be converted to dimers Cu2(dppm)2(dmcn)3(BF4)2 and Cu2(dppm)2(dmcn)(Cl)2 by reaction with HBF4, dmcn, and excess dmcn, respectively. The complexes synthesized by the above means, Cu3(dppm)3(μ3-Cl)2ClO4 (1), Cu3(dppm)3(μ3-Br)2ClO4 (2)·2THF, Cu3(dppm)3(μ3-I)2I· 2CH2Cl2·CH3OH (3), and Cu2(dppm)2(dmcn)(Cl)2·2dmcn (4) have been characterized by IR, 1H and 31P{1H} NMR, and solid-state emission spectroscopy. The solid-state molecular structures of complexes 2, 3, and 4 were determined from single-crystal X-ray diffraction studies. Apart from confirming the nuclearity, the structural information reveals interesting variations in the Cu···Cu distance...