The concept of specific microwave effects in solid/liquid catalytic processes resulting from the selective heating of a microwave-absorbing heterogeneous transition-metal catalyst by using 2.45 GHz microwave irradiation was evaluated. As model transformations Ni/C-, Cu/C-, Pd/C-, and Pd/Al2O3-catalyzed carbon–carbon/carbon–heteroatom cross-couplings and hydrogenation reactions were investigated. To probe the existence of specific microwave effects by means of selective catalyst heating in these transformations, control experiments comparing microwave dielectric heating and conventional thermal heating at the same reaction temperature were performed. Although the supported metal catalysts were experimentally found to be strongly microwave absorbing, for all chemistry examples investigated herein no differences in reaction rate or selectivity between microwave and conventional heating experiments under carefully controlled conditions were observed. This was true also for reactions that use low-absorbing or microwave transparent solvents, and was independent of the microwave absorbtivity of the catalyst support material. In the case of hydrogenation reactions, the stirring speed was found to be a critical factor on the mass transfer between gas and liquid phase, influencing the rate of the hydrogenation in both microwave and conventionally heated experiments.