Hydrolysis of 5-cyanovaleramide (5-CVAM) in near-critical water without the addition of any catalyst has been demonstrated. The results demonstrated that the cyano group at one end of the carbon of 5-CVAM is more reactive than the amide group at the other end, under the same experimental conditions. The relations between 5-CVAM concentration and residence time revealed that hydrolysis of 5-CVAM shows second-order reaction kinetics in the investigated temperature range. The rate constants, average apparent activation energy and pre-exponential factor were evaluated according to the Arrhenius equation. Based on the experimental results, a carbon balance was calculated, and a hydrolysis reaction scheme of 5-CVAM was proposed.