AbstractThree new BPTA‐bridged binuclear copper(I) complexes bearing three different diphosphine ligands, namely, [(CuI)2(Xantphos)2(BPTA)](BF4)2 (Cu1), [(CuI)2(Dppp)2(BPTA)](BF4)2 (Cu2), and [(CuI)2(Binap)2(BPTA)](BF4)2 (Cu3), have been synthesized and characterized. The X‐ray structure analyses of complex Cu3 show that the central copper(I) ion adopts a distorted tetrahedral geometry. Complexes Cu1 and Cu2 exhibit greenish‐yellow emission with excited‐state lifetime (13μs and 27μs) and photoluminescence quantum yields (6.86 % and 0.62 %) at room temperature in the solid state. Emission decay measurement and theoretical calculation suggest that the transition nature of their emission could be assigned to 3MLCT/3LC excited states. More interesting, complexes Cu1‐Cu3 are weakly emissive in solution but become strongly luminescent in solid state, so it has the aggregation induced emission (AIE) behavior.