The [2 + 3] cycloaddition reactions (which are greatly accelerated by microwave irradiation) of the di(azido)platinum(II) compounds cis-[Pt(N-3)(2)(PPh3)(2)] (1) with cyanopyridines NCR (2) (R = 4-, 3-, and 2-NC5H4) give the corresponding bis(pyridyltetrazolato) complexes trans-[Pt(N4CR)(2)(PPh3)(2)] (3) [R = 4-NC5H4 (3a), MCA (3b), and 2-NC5H4 (3c)]. Compound 3c has been characterized as the (NN2)-N-1-bonded isomer in the solid state by X-ray crystallography and represents the first bis(tetrazolato) complex of this kind. Complexes 3a and 3b have been used as metallaligands to generate heteronuclear coordination polymers in the presence of copper nitrate. A one-dimensional supramolecular architecture was obtained as the exclusive product, {trans-[Pt-2(N4CR)(4)(Pph(3))(4)Cu]n(NO3)(2)n center dot nH(2)O (4 center dot nH(2)O) (R = 4-NC5H4), when 3a was employed, whereas with 3b the heteronuclear square complex {trans[Pt(N4CR)(2)(PPh3)(2)CU(NO3)(2)(H2O)](2) (5) (R = 3-NC5H4), composed of Pt/Cu ions, was obtained. All the isolated complexes were characterized by IR, elemental, and (for 3b, 3c, 4, and 5) X-ray structural analyses. Complexes 3 were additionally characterized by H-1, C-13, and P-31 {H-1} NMR spectroscopies.