The influence of electronic and geometric factors is considered in the context of the manifestation of size effects in heterogeneous catalytic oxidation and hydrogenation reactions. Both of the factors are interdependent; however, the electronic factor predominates with regard to small metal and metal oxide particles (smaller than 10 nm), for which the energies of electron transitions in an activated complex are size-dependent. Only the geometry of active component nanoparticles exerts the main effect on the catalytic properties of coarser particles. In this case, the geometric factor depends on the accessibility of the active surface to reactants. The probability of the occurrence of complex active centers including several surface atoms increases as the active component particles of a catalyst become larger. The efficiency of the approach proposed to study the activating effect of nanophase catalysts is demonstrated using the oxidation and hydrogenation reactions of carbon oxides and the hydrogenation of acetonitrile and acetone as examples.