Herein, the complete active space self-consistent field (CASSCF) and its second-order perturbation (CASPT2) methods combined with time-dependent density functional theory (TD-DFT) calculations were employed to investigate the isomerization reaction mechanisms of an asymmetric N,C-chelate organoboron compound, B(ppy)MesPh, in the ground (S₀) state and the first singlet excited (S₁) state. Our calculations show that isomerizations proceed via different pathways in the S₀ and S₁ states,; however, the energy barriers for mesityl isomerization are higher than those for phenyl isomerization in both states; this is in good agreement with the experimentally observed regioselectivity (S. Wang, et al. Angew. Chem., Int. Ed., 2017, 56, 6093–6097). Photoisomerization is motivated by charge transfer from two phenyl rings to the pyridyl moiety and initiated by the cleavage of the B–C_ppy bond, followed by the formation of a boracyclopropane ring via an (S₁/S₀)_X conical intersection and a biradical intermediate. Both steric and electronic features were found to be important for regioselective photoisomerization. Our results not only shed light on the experimental observations, but also provide valuable details on the excited state dynamics of organoboron compounds and can facilitate further syntheses and applications.