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.,　[(PPh3Me)(Cu3I4)]n　(1),　[(PPh3Et)(Cu3I4)]n　(2),　(PPh3iPr)2(Cu2I4)　(3),　[(PPh3nBu)(Cu3I4)]n　(4).　The　inorganic　iodocuprates　in　1,　2　and　4　are　1-D　(Cu3I4)n　n–　chains　constructed　from　Cu5I11　units,　but　(Cu2I4)2–　in　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　organic　and　inorganic　moieties　and　as　a　result,　inhibit　hydrolysis　reaction.　Furthermore,　all　compounds　exhibit　typical　reversible　luminescent　thermochromic　behaviors,　among　which　4　exhibits　blue　emission　and　the　quenching　of　higher　energy　(HE)　zone　in　1　and　2　are　led　by　strong　π–π　stacking　interactions.　Besides,　effective　and　repeatable　photocurrent　responses　can　be　detected　in　these　compounds.　In　all,　by　systematically　introducing　alkyl　groups　into　(triphenyl)phosphonium　as　SDAs　to　prepare　hybrid　iodocuprates,　we　can　find　that　the　longer　alkyl　groups　can　achieve　stronger　tunable　PL　materials　with　enhanced　water　stabilities.　©　2018　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim