Despite extensive experimental and theoretical studies on the kinetics of the O(3P) + C7H8 (toluene) reaction and a pioneering crossed molecular beam (CMB) investigation, the branching fractions (BFs) of the CH3C6H4O(methylphenoxy) + H, C6H5O(phenoxy) + CH3, and spin-forbidden C5H5CH3 (methylcyclopentadiene) + CO product channels remain an open question which has hampered the proper inclusion of this important reaction in the chemical modelling of various chemical environments, such as toluene combustion. We report a CMB study with universal soft electron-ionization mass-spectrometric detection of the reactions O(3P,1D) + toluene at the collision energy of 34.7 kJ/mol. From CMB data we have inferred the reaction dynamics and quantified the BFs of the primary products and role of intersystem crossing (ISC). The CH3 elimination channel dominates (BF = 0.690.22) in the O(3P) reaction, while the H-displacement and CO formation channels are minor (BF = 0.220.07 and 0.090.05, respectively), with ISC accounting for more than 50% of the reactive flux. Synergistic transition-state theory (TST)-based master equation simulations including nonadiabatic TST on ab initio coupled triplet/singlet potential energy surfaces were employed to compute the product BFs and assist the interpretation of the CMB results. In the light of the good agreement between the theoretical predictions for the O(3P) + toluene reaction and the CMB results as well as the absolute rate constant as a function of temperature (T) (from literature), the so validated computational methodology was used to predict channel-specific rate constants as a function of T at 1 atm.