The extraction of vanillin (4‐hydroxy‐3‐methoxybenzaldehyde) from water medium with octylamine solution in heptane was studied. The distribution ratios were found to increase with the octylamine concentration and to attain values up to 600. The slope of the logarithmic dependence of the distribution ratios versus octylamine concentration is equal to 1.62±0.14. In the organic phase, the vanillin molecule reacts with octylamine by both phenolic and carbonyl groups forming the Schiff base RN˭CH‐Ar‐OH…NH2R. The structure of the compounds formed was confirmed by 1H NMR spectroscopy.