The syntheses and luminescent properties of three novel zinc coordination polymers containing tetrazolyl ligands are described. In situ [2+3] cycloaddition reactions of acetonitrile or p-tolylnitrile with sodium azide in the presence of Zn(ClO4)(2) as a Lewis acid (Demko-Sharpless tetrazole synthesis method) under hydrothermal (solvothermal) reaction conditions gave [Zn(CH3CN4)(2)](3)(H2O) (1) and [Zn(4-MPTZ)(2)] (3) [4-MPTZ = 5-(4-methylphenyl)tetrazole], respectively. On the other hand, [Zn(HCN4)(2)] (2) was obtained by directly reacting tetrazole with Zn(OAC)(2) under hydrothermal reaction conditions. The structure of 1 shows a super-diamond-like topological network with a diamond subunit as a connecting node. For 2, a diamond-like topological network is also found, but it is 2-fold interpenetrated. The structure of 3 reveals a 2D layered network with a hexagonal net, with the adjacent layers in the network stacked in an ABAB sequence. Photoluminescence studies revealed coordination polymers 1, 2, and 3 exhibit strong blue fluorescent emissions at Am, = 396, 418, and 397 nm, respectively, in the solid state at room temperature.