A series of unprecedented cationic copper(i)-iodide aggregates, (Cu4I2)2+, (Cu6I2)4+ and (Cu10I4)6+, are trapped in the in situ formation of anionic-tetrazolate-based coordination polymers, namely [Cu2(mu3-I)(mu5-Cpta)]n (1), [Cu5(mu4-I)(mu4-Mtta)3(CN)]n (2) and [Cu5(mu6-I)(mu2-I)(mu4-Mtta)3](n) (3) [Cpta = 5-(3-cyanophenyl)tetrazolate, Mtta = 5-methyltetrazolate], which exhibit structure-related green, cyan and blue luminescence, respectively.