The coordination ability of the pyridine derivative of cyclic triimidazole, namely 3-(pyridin-2-yl)triimidazotriazine (TT-Py) towards Cu(I) was explored. TT-Py is an appealing nitrogen-rich ligand characterized by the presence of three imidazole nitrogen atoms with trigonal symmetry and a pyridine moiety, available for coordination to metal ions. The multidentate nature of TT-Py allows to isolate, by reaction with CuI at room temperature, the one-dimensional coordination network [Cu2I2(TT-Py)]n (1). 1 is characterized by a rare structural network built-up by the combination in a 1:2 ratio of two common motifs for Cu(I) halides coordination polymers, which are the double-stranded stair and the zig-zag chain. 1 displays one broad long-lived emission in the solid state, which has been associated, by the support of DFT and TDDFT calculation, with low-energy transitions of MLCT or XMLCT character.