The photochemical C-H activation reactions of eta(3)-Tp*Rh(CO)(2) (Tp* = HB-Pz(3)*, Pz* = 3,5-dimethylpyrazolyl) and CpRh(CO)(2) (Cp = C5H5) have been studied in a series of linear, cyclic, and aromatic hydrocarbon solvents on a femtosecond to microsecond time scale. These results have revealed that the structure of the hydrocarbon substrate affects the final C-H bond activation step, which is in accordance with the known preference of bond activation toward primary C-H sites. In the case of aromatic C-H activation, the reaction is divided into parallel channels involving sigma- and pi-solvated intermediates. Results for the analogous CpRh(CO)(2) molecule have shown that the coordination of the cyclopentadienyl ligand does not play a direct role in the dynamics of the reaction, in contrast to the C-H activation mechanism observed in eta(3)-Tp*Rh(CO)(2) studies.