A class of zinc α-ketoacidoximates have been prepared as precursors for the single source chemical vapour deposition of ZnO thin films. The X-ray structures of this class of compounds have been elucidated for the first time and show interesting structural variations relating to ligand substituents, which also influence the thermal stability and sublimation yield of these complexes. Zinc complexes of pyruvic and glyoxylic acid oximes have been investigated as potential precursors for single source chemical vapour deposition (SSCVD) of ZnO thin films. The X-ray crystal structures of the complexes and of their -NOMe analogues reveal markedly different coordination and intermolecular bonding patterns. These structural differences, in conjunction with ligand substituent changes impart different responses to thermogravimetric analysis (TGA), and sublimation. The glyoxylic acid methyloxime Zn(O 2CCHN(OMe)) 2 • 2H 2O has volatility and thermolysis properties suitable for SSCVD of ZnO.