The rhodium(I)-catalyzed reaction of N-8-aminoquinolinyl aromatic amides with maleimides results in C-H alkylation at the ortho position of the amide. The reaction path and formation of the alkylation product with density functional theory (DFT) calculations were done. The detailed computational study showed that the reaction proceeds in the following steps: (I) deprotonation of the NH amide proton, (II) oxidative addition of the ortho C-H bond, (III) migratory insertion of the maleimide, (IV) reductive elimination with the C-C bond formation, and (V) protonation. The energetic span model showed that the turnover frequency (TOF)-determining transition state (TDTS) is the oxidative addition, while the TOF-determining intermediate (TDI) is the formation of an Rh(I)-complex after N-H deprotonation. It was also found that the change in the oxidation number of the Rh catalyst is a key determinant of the reaction path.