Alkyl-xanthato gallium(III) complexes of the form [Ga(S2COR)3] where R= Me (1), Et (2), iPr (3), nPr (4), nBu (5), sBu (6) and iBu (7) have been synthesized and fully characterised. Crystal structures for 1 and 3-7 have been solved and their structures examined to elucidate if their structure is related to their decomposition. Thermogravimetric analysis was used to give insight into the decompostion temperatures for every complex. Unlike previously explored metal xanthate complexes which break down at low temperatures (< 250 °C), to form crystalline metal chalcogenides, powder X-ray diffraction measurements suggest that when R ≥ Et thesecomplexes did not produce crystalline gallium sulfide until heated to 500 °C, where the γ-Ga2S3 was the sole product formed. In the case of R = Me Chugeav elimination is unable to occur and amphorphous GaxSy products were formed. We conclude therefore that the low temperature synthesis route offered by the thermal decompsoition of metal xanthate precursors, which has been reported for many metal sulfide systems prior to this, may not be appropriate in the case of gallium sulfides.