The synthesis of a novel silver(I) coordination polymer based on a bis 1,2,4-triazole derivative, namely {[Ag(L)](NO3)}n (1, L = 1,4-bis(1,2,4-triazolyl-3-sulfanylmethyl)benzene), has been reported. The silver(I) complex has been characterized by FT-IR-, 1H NMR-spectroscopy, mass spectrometry, and elemental analysis. The crystal structure of 1 has been determined by single-crystal X-ray diffraction. According to the determined molecular structure of 1, its structure can be described as a layer package. The thermal behavior of the synthesized complex has also been investigated. The pyrolysis product of complex 1 was characterized as a highly pure, uniform silver nanosheets (thickness: ca. 35 nm) using a series of techniques including X-ray powder diffraction, energy-dispersive X-ray, and scanning electron microscopy. The remarkable advantage of this approach is to fabricate the desired Ag nanostructure using a convenient metal complex.