We report here the hydrogenation of cycloalkenes using Rh-supported montmorillonite as a catalyst. The catalyst preparation was based on oxidative degradation of intercalatedtris(phenanthroline)-Rh (III) followed by reduction under hydrogen atmosphere. No obvious trend is seen in the hydrogenation yields of the olefins though cyclopentene and cyclooctene are reduced faster than cyclohexene and cycloheptene. 2-Cyclohexen-1-one reacts marginally faster than cyclohexene under similar conditions. When the hydrogenation experiments were repeated employing binary mixtures of the olefins, considerable differences in hydrogenation behaviour were observed over that found when the olefins were taken in their pure form. The most notable difference in the hydrogenation behaviour of binary mixtures was observed in the case of cyclopentene/cyclooctene: both olefins could be efficiently hydrogenated in their pure form but there was no conversion of cyclooctene in presence of cyclopentene.