A series of rhodium(III) bis(quinolinyl)benzene (bisqx) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisqx) ligand candidates involving different functional groups to determine the impact on RhIII(bisqx)‐catalyzed methane functionalization. The free energy activation barriers for methane CH activation and Rh–methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is RhIII coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η2‐benzene coordination mode of (bisqx) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.