Hypercrosslinked polystyrene (HPS) has been used as a support for preparation of the palladium-based catalyst, Pd/HPS, for gas phase hydrogenation of phenol to cyclohexanone. At the phenol conversion 99%, the catalyst provides selectivity for ketone not lower than 95 mol%. The Pd/HPS catalyst showed high stability, retaining its catalytic performance at least for 20 days. Kinetics was used to compare Pd/HPS with the commercial Pd/Al2O3 catalyst. The catalytic efficiency was assessed using the derived dimensionless kinetic equation without a 'time' parameter. Three major reaction routes with their rate parameters and activation energies were revealed. From kinetic parameters, the maximum possible yield of cyclohexanone in the temperature range of 120-180 degrees C was determined. The important feature of the Pd/HPS catalyst is that selectivity is independent of the temperature at a certain phenol conversion. At elevated temperatures (160-180 degrees C). the selectivity is at least 2-3% higher as compared to the commercial catalyst Pd/Al2O3, which makes Pd/HPS largely promising for industrial applications. (C) 2011 Elsevier B.V. All rights reserved.