The photophysics of two α,β-carboxylic methyl esters after excitation to the light absorbing S2(ππ(*)) state were studied by using the resonance Raman spectroscopy and complete active space self-consistent field (CASSCF) method calculations. The vibrational spectra were assigned on the basis of the experimental measurements and the B3LYP/6-31G(d) computations, as well as the normal mode analysis. The A-band resonance Raman spectra of methyl 2,4-pentadienoate (M24PDA) and methyl trans cronoate (MTCA) were measured to probe the structural dynamics in Franck-Condon region. CASSCF calculations were done to obtain the minimal excitation energies and geometric structures of the lower-lying singlet and triplet excited states, and the curve-crossing points. It was revealed that the short-time structural dynamics of M24PDA was dominated by the Cα=Cβ-C4=C5 stretch coordinate, while that of MTCA was mostly along the Cα=Cβ and the C=O stretch motion. Comparison of the structural dynamics of M24PDA and MTCA with that of 3-methyl-3-pentene-2-one (3M3P2O) indicated that the structural dynamics of MTCA is similar to that of 3M3P2O but different than that of M24PDA in that the variation of the Raman intensity ratios for ν7/ν8, (ν7+ν8)/2ν8, (ν7+2ν8)/3ν8, (ν7+3ν8)/4ν8 of MTCA is similar to that of 3M3P2O but different from that of M24PDA. It is found that the substitution of methyl group in the α(')-position of α,β-enones by methoxyl group does not substantially affect the short-time structural dynamics, while the substitution of vinyl group in the β-position changes significantly the short-time structural dynamics and the subsequent decay processes. A detailed decay mechanism is proposed. Two sub-processes which consider the reconjugation and the subsequent charge-transfer reaction of O=C-Cα=Cβ chromophore were postulated to describe the variation of short-time structural dynamics with the different substitution.