o-Nitrobenzyl (oNB) derivatives are widely used photolabile caged compounds in chemical and biological applications. The primary step in the photoinduced deprotection is an excited state intramolecular hydrogen transfer (ESIHT) leading to tautomerization of the oNB compound and subsequent release of the protecting group. The prototype molecule for studying such ESIHT is o-nitrotoluene (oNT), where hydrogen transfers from the methyl to the intro group. Using the complete active space self-consistent field (CASSCF) method with second-order perturbative energy corrections (CASPT2), we have comprehensively investigated the photoisomerization and photo decay mechanisms in oNT. We have obtained the minimum energy crossing points (MECPs) between relevant electronic states and identified the singlet and triplet pathways. There is a barrierless path for oNT to relax to the lowest triplet state. In this T-1 state, the ESIHT products are more stable than T-1 oNT. Hydrogen-transfer occurs on the T-1 state followed by relaxation to the ground state to give the isomerized product. A biradical intermediate proposed by previous studies is characterized to be the hydrogen-transferred T-1 product. On the singlet pathway, in contrast to the triplet, the ground state tautomer is formed from the S-1 oNT through a geometrically distant and energetically higher S-1/S-0 conical intersection. Although nonadiabatic dynamical studies are essential for determining branching ratios, our study, which considers the accessibility of different MECPs based on geometry and energy, and the magnitude of spin orbit coupling at singlet triplet MECPs, suggests that a significant fraction of the isomerization yield is due to the triplet channel.