Organic complexing agents have received special attention over the past few decades in the search for reagents for improved flotation separation of minerals, especially non-sulphides. The majority of such reagents that have been proposed over the past few decades have remained largely a laboratory curiosity, except perhaps alkyl hydroxamates, because their selection is seldom based on commercial viability. In this regard, the choice of complexing agents such as oximes may be more realistic because of their widespread use in solvent extraction of copper. Our earlier studies have confirmed that they are also effective as collectors for copper oxide minerals, including chrysocolla which is the most difficult copper mineral to beneficiate. The flotation behaviour of chrysocolla for several structurally-related hydroxyoximes were studied as a function of pH and oxime concentration and the role of structural features examined. The structural changes studied included substitutions in both chelating and non-chelating parts of the molecule. The results indicated that, contrary to expectations, many of the structural changes in the basic molecule, salicylaldoxime, do not have a positive effect on collector efficiency. The reduction in collector efficiency is rationalised on the basis of possible steric factors affecting complexation and packing of the collector species on the mineral surface as well as effects due to changes in electron density brought about by substituents. Introduction of alkyl substituents on the oximic carbon of salicylaldoxime yielded the highest collector efficiency.