The regularities of extraction of adsorbate from spent bleaching earth (SBE) of sunflower oil by the esteraldehyde fraction (EAF) have been established. The content of the substances adsorbed by SBE was 34.1%, including 19.2% free fatty acids (FFA) and 11.1% moisture. The influence of temperature (50 and 700C), extraction duration (60 and 120 min), and the mass ratio of EAF to SBE ((2–4):1) on the extraction parameters has been determined. It was found that increasing these process parameters enhances the extraction degree of the adsorbate and FFA from the bleaching earth, reaching 41.9% and 34.4%, respectively, at a temperature of 700C, extraction duration of 120 min, and a mass excess of EAF to SBC at a ratio of 4:1. Optimal conditions for the removal of FFA from SBE were identified. It was established that strong acidic sites are present on the surface of the bleaching earth, with the acidity of fresh, spent, and EAF-treated bleaching earth being 0.79, 0.77, and 0.74 mmol H+ per gram, respectively. The basicity of fresh bleaching earth was 0.073 mmol OH– per gram, indicating the ability of bleaching earth to catalyze the esterification of FFA with ethanol. The suitability of the obtained extract for the production of FFA ethyl esters was demonstrated.