Although a number Of acentric; or chiral tetrazole complexes were synthesized from Sharpless reaction, there are no spontaneous resolution Cu(I)-tetrazole compounds from in situ [2 + 3] cycloaddition synthesis that have been reported before. The first enantiomers Delta- and Lambda- of metal tetrazole compound [Cu(Tzmp)](n) (1) (HTzmp = 3-tetrazolemethylpyridine) were obtained and isolated from in situ [2 + 3] cycloaddition reactions of a flexible organic nitrile (3-cyanomethylpyridine) with sodium azide in the presence of CuCl2 as the Lewis acid. Delta-1 and Lambda-1 feature a homochiral helical coordination polymeric system and {4(4).6(2)} two-dimensional framework. The photoluminescence Study suggests 1 exhibits strong green fluorescence in solid state With maximal emission peaks around 535 nm. Remarkably, the Delta- and Lambda- of [Cu(Tzmp)](n) (1) catalyzes the enantioselective Henry reaction with high yield (More than 96%) and certain enantioselectivity (up to 69%).