The toxicological relevance and widespread occurrence of fatty acid esters of 2-chloropropane-1,3-diol (2-MCPD) and 3-chloropropane-1,2-diol (3-MCPD) in refined oils and fats have recently triggered an interest in the mechanism of formation and decomposition of these contaminants during oil processing. In this work, the effect of the main precursors, namely acylglycerols and chlorinated compounds, on the formation yield of MCPD esters was investigated in model systems simulating oil deodorization. The composition of the oils was modified by enzymatic hydrolysis, silica gel purification and application of various refining steps prior to deodorization (namely degumming, neutralization, bleaching). Partial acylglycerols showed greater ability, than did triacylglycerols, to form MCPD esters. However, no direct correlation was found between these two parameters, since the availability of chloride ions was the main limiting factor in the formation reaction. Polar chlorinated compounds were found to be the main chloride donors, although the presence of reactive non-polar chloride-donating species was also observed.