Unimolecular reactions of alkylperoxy(ROO•), hydroperoxyalkyl(•QOOH), and hydroperoxyalkylperoxy(•OOQOOH) radicals of 2-butanone, which is a potential biofuel molecule, have been studied computationally. These radicals are responsible for the chain branching at low temperature oxidation and play a significant role in modeling the autoignition. The composite CBS-QB3 method was used to study the thermochemistry and energetics of all the species involved. Intrinsic reaction coordinate (IRC) calculations were carried out for all the transition states along various reaction pathways. All the possible reactions like H-migration, •OH elimination, and HO•2 elimination reactions were studied for these radicals. It was found that, the isomerization of •OOQOOH to HOOQOO• is the most favorable channel, which involves 8- and 9-membered cyclic transition states. However, the decomposition pathway involves the H-migration from carbon to oxygen. The mechanism for the decomposition of all •OOQOOH radicals with their potential energy level diagrams are reported. The temperature dependent rate coefficients were also studied using Canonical Variational Transition state theory (CVT) with small curvature tunneling (SCT) in the temperature range of 400–1500 K, which is relevant to the combustion. Thermodynamic parameters for all the reactions involved were calculated. The high barrier (1,3 H-migration) reactions were found to be exothermic and spontaneous, which is unexpected.