Tin aminothiolate compounds SnII(dmampS)2 (1) and SnIV(dmampS)2Se (2), where dmampS = 1-(dimethylamino)-2-methylpropane-2-thiolate, were synthesized. The molecular structures of 1 and 2 reveal a seesaw and distorted trigonal-bipyramidal geometry, respectively. The 1H NMR spectrum of 1 shows two types of resonances for the methyl groups of the α-carbon, methyl groups of the amino groups, and methylene groups at room temperature. On the other hand, the 1H NMR spectrum of 2 exhibits a single resonance for each of these groups. According to variable-temperature 1H NMR analysis, each of these two types of resonances occurring at relatively low temperatures (under 223 K for 1 and under 333 K for 2) are merged as a single resonance with increasing temperature. By using thermogravimetric and thermal decomposition analyses, the residual materials of compounds 1 and 2 are confirmed to be SnS and SnSSe, respectively. Compound 1 was subjected to a metal-organic chemical vapor deposition process, which allowed for the deposition of a dense and well-faceted orthorhombic phase SnS thin film on a SiO2/Si substrate with ∼200 nm thickness.