The unimolecular dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonylmethyl (CH2C(=O)OCH3) and acetyloxylmethyl (CH3C(=O)OCH2) are theoretically investigated using high-level ab initio methods and the Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) theory. Potential energy surfaces (PESs) are obtained using coupled cluster singles and doubles with perturbative triples correction (CCSD(T)), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson-Silver (DS) correction, and multireference averaged coupled pair functional (MRACPF2) theory. The transition states exhibit high T1 diagnostics in coupled cluster calculations, suggesting the need for a multireference correlated wave function treatment. MRSDCI+DS and MRACPF2 capture their multiconfigurational character well, yielding lower barrier heights than CCSD (T) for these reactions. The rate coefficients are computed using the RRKM/ME theory over a 500-2500 K temperature range and at a pressure range of 0.01 atm to the high-pressure limit. The temperature- and pressure-dependent rate coefficients are given in modified Arrhenius expressions. The beta-scission of CH2C(=O)OCH3 is predicted to have a much higher barrier than the corresponding isomerization reaction and the beta-scission of CH3C(=O)OCH2. Consequently, the rate coefficients for beta-scission of CH2C(=O)OCH3 are the smallest among the three reactions and the isomerization followed by decomposition to CH3C(=O) and HCHO is the dominant reaction pathway for CH2C(=O)OCH3. Both radicals CH2C(=O)OCH3 and CH3C(=O)OCH2 are predicted to mainly decompose to CH3C(=O) + HCHO rather than to the bimolecular product CH2C(=O) + CH3O. A newly developed MA combustion mechanism, using our theoretical rate coefficients for the MA-related reactions, predicts combustion properties in good agreement with available experimental data.