The amidation of long‐chain fatty acids is the key step for preparing surfactants with excellent interfacial activity. Gas chromatography–mass spectrometry was employed to detect the reactants and products in the direct amidation reactions. The conversion and the concentration of the amides in the reaction process were also investigated to determine the best catalyst, the reaction rate constants, and activation energy. It was identified that the amidation reaction of the long‐chain phenyl fatty acid was a zero‐order reaction and 3,4,5‐trifluorophenylboronic acid was the most effective catalyst by which the activation energy reduced to 55.79 kJ/mol from 95.44 kJ/mol. The method can be applied to other long‐chain fatty acids, saturated or unsatureated. The turning‐over‐temperature was 156°C, over which high yields can be achieved without any catalyst. These provide a reference for the preparation of long‐chain fatty acid amides.