Two　new　copper(i)　iodide-based　hybrids,　i.e.　(Py3P-O-PPy3)(Cu2I4)　(1)　and　(Py3P-O-PPy3)(Cu4I6)　(2)　(Py　=　pyrrolidine),　have　been　prepared,　in　which　the　tripodal　diphosphonium　(Py3P-O-PPy3)(2+)　is　in　situ　generated　in　the　one-pot　synthesis.　The　disordered　(Cu4I6)(2-)　tetramers　are　rare　with　two　sets　of　tetracuprate　centers.　Interestingly,　1　exhibits　sensitive　luminescence　mechanochromism,　which　is　ascribed　to　the　disturbed　cuprophilic　Cu...Cu　interactions　and　the　crystalline　packing　adjustment　by　destroying　C-H...I　hydrogen　bonds　during　mechanical　force.　In　particular,　the　luminescence　thermochromism　is　unique,　whose　fluorescence　intensity　is　strengthened　with　the　elevated　temperature.　This　could　be　due　to　the　S-2-S-1　internal　conversion　on　the　linear　P-O-P　backbone,　which　will　be　bent　upon　heating.　Simultaneous　luminescence　thermo/mechanochromism　can　also　be　monitored　in　1.　However,　no　luminescence　thermo/mechanochromic　performances　can　be　detected　in　2,　so　the　luminescence　thermo/mechanochromism　of　1　could　be　quenched　with　DMF.　The　conclusions　in　this　work　might　provide　a　new　large-scale　synthesis　strategy　for　intelligent　responsive　luminescent　materials.