ABSTRACTLiquid polyesters of raffinose (raffinose polyesters, RPE) were synthesized by a one‐stage solvent‐free interesterification of raffinose un‐decaacetate (RUAC) and fatty acid methyl esters (FAME) of salad oils, long chain fatty acids and blends thereof. Interesterification was essentially a low temperature, low pressure process consisting of forming a homogenous melt of RUAC and FAME in the presence of an alkali metal catalyst (2 sodium). RPE were formed with 95.8–99.3 yield based on initial weight of RUAC. Formation of RPE was evaluated with thin layer chromatography (TLC) and RPE composition determined by transesterification with 1.0 M methanolic NaOH, followed by TLC and gas liquid chromatography (GLC). The structure of RPE was confirmed by both infrared (IR) and nuclear magnetic resonance (C‐13 NMR) spectroscopy. Physical properties of the synthesized RPE were similar to physical properties of sucrose polyesters (SPE), conventional salad and vegetable oils. Synthesis of RPE catalyzed by sodium metal appeared to be a deacetylation‐acylat
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