Four (triphenyl)phosphonium-based quaternary phosphorus salts with different substituents (varying from methyl to n-butyl) were selected to be structural directed agents (SDAs) to construct four iodocuprate(I) hybrids via solution method, i.e., [(PPh 3 Me)(Cu 3 I 4 )] n (1), [(PPh 3 Et)(Cu 3 I 4 )] n (2), (PPh 3 iPr) 2 (Cu 2 I 4 ) (3), [(PPh 3 nBu)(Cu 3 I 4 )] n (4). The inorganic iodocuprates in 1, 2 and 4 are 1-D (Cu 3 I 4 ) n nchains constructed from Cu 5 I 11 units, but (Cu 2 I 4 ) 2in 3 is a di-nuclear cluster. Interestingly, the strength of Cu···Cu and π-π stacking interactions are weakened with the lengthening of alkyl groups on P-atom. The best water stability of 4 can be ascribed to the better hydrophobicity of n-butyl group, which deters the dispersing of [a]