A novel tin(II)-compound, bis(η2-N,O-2-[4,5-dimethyloxazolyl]-1,1,1-trifluoro-propen-2-olato)tin, SnII[(Me2C3NO)(CHCOCF3)]2 (1), was obtained by reacting Sn[N(SiMe3)2]2 with 2M equivalents of the β-heteroarylalkenol, (Me2C3NO)(CHCOHCF3) (2). The molecular structures of ligand and the tin derivative were elucidated by single crystal X-ray diffraction and multi-nuclear NMR spectroscopic studies, which confirmed the monomeric nature and fourfold coordination of the tin(II) center with a pseudo-pyramidal geometry. The bidentate chelating mode of 2 imparted intriguingly high air stability to 1, which together with its high volatility make it an interesting precursor for the chemical vapor deposition (CVD) process. CVD of 1 on gold-coated Al2O3 substrates produced single crystalline SnO2 nanowires by vapor–liquid–solid growth mechanism. Transmission electron microscopy studies and X-ray diffraction data confirmed the high crystallinity of SnO2 nanowires possessing an average diameter of 90nm.