Abstract The kinetics of the gas‐phase elimination of benzaldoxime was determined in a static reaction system over the temperature and pressure range 350°C–400°C and 56–140 Torr, respectively. The products obtained were benzonitrile and water. The reaction was found to be homogeneous, unimolecular, and tend to obey a first‐order rate law. The observed rate coefficient is represented by the following Arrhenius equation: equation image According to kinetic and thermodynamic parameters, the reaction proceeds through a concerted, semi‐polar, four‐membered cyclic transition state type of mechanism. © 2007 Wiley Periodicals, Inc. 39: 145–147, 2007