Sequential-cooling urea–fatty acid complexation is a novel technique developed to pre-concentrate vitamin E extracted from palm fatty acid distillate before further purification by supercritical fluid extraction. The efficacies of the sequential-cooling and the constant cooling methods were compared. The sequential-cooling method cools the reaction mixture to a sequence of predetermined temperatures between 35°C and -5°C, whereas the constant cooling method cools down to −5°C that is maintained for 12 hours. The recovery of vitamin E was increased from 21.62% with constant cooling to 32.04% with sequential cooling, while the corresponding concentration in the sample increased from 8.85 to 25.16 % (w/w). Combining sequential cooling urea– fatty acid complexation with a final supercritical fluid extraction increased the concentration of vitamin E to 80%.