The unimolecular dissociation and isomerization kinetics of the three methyl propanoate (MP) radicals, CH<
sub>
3<
/sub>
CH<
sub>
2<
/sub>
C(=O)O$\dot{C}$H<
sub>
2<
/sub>
(MP-m), CH<
sub>
3<
/sub>
$\dot{C}$HC(=O)OCH<
sub>
3<
/sub>
(MP-?), and $\dot{C}$H<
sub>
2<
/sub>
CH<
sub>
2<
/sub>
C(=O)OCH<
sub>
3<
/sub>
(MP-?), are theoretically investigated using high-level ab initio methods and the Rice?Ramsperger?Kassel?Marcus (RRKM)/master equation (ME) theory. Stationary-point energies are obtained using the coupled cluster singles and doubles with perturbative triples correction (CCSD(T)), multi-reference singles and doubles configuration interaction (MRSDCI) with the Davidson-Silver (DS) correction, and multi-reference averaged coupled pair functional (MRACPF2) theories. The isomerization barriers between the three radicals are predicted to be generally lower than the corresponding bond dissociation channels, leading to a strongly coupled reaction system in subsequent kinetics studies. The phenomenological temperature- and pressure-dependent rate coefficients are computed using the RRKM/ME theory over a temperature range of 500 to 2000 K and at a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. The ?-scission rate coefficients of MP-? to CH<
sub>
3<
/sub>
CHC(=O) and CH<
sub>
3<
/sub>
$\dot{O}$ are predicted to be the smallest because of its highest activation energy among all studied unimolecular reactions channels. Analysis of branching fractions shows that both MP-m and MP-? radicals mainly decompose to the bimolecular products CH<
sub>
3<
/sub>
CH<
sub>
2<
/sub>
$\dot{C}$(=O) and H<
sub>
2<
/sub>
CO, whereas the MP-? radical primarily decomposes via cleavage of a C?C bond to form C<
sub>
2<
/sub>
H<
sub>
4<
/sub>
and CH<
sub>
3<
/sub>
O$\dot{C}$(=O). The isomerization channels dominate at low temperatures, the branching fractions of which decrease with increasing temperature and become very minor at about 2000 K. Our accurate rate coefficients and branching fractions help to illuminate the unique combustion properties of MP.