A double resonance scheme was employed to photodissociate jet-cooled CH3CF2Cl in a time-of-flight mass spectrometer. First, the molecule was promoted to the second (3nu(CH)) or third (4nu(CH)) methyl overtone by direct IR excitation. Subsequently, a UV laser beam at similar to235 nm was used to both dissociate the molecule and tag the Cl P-2(3/2) [Cl] and Cl (2)p(1/2) [Cl*] photofragments by(2 + 1) resonantly enhanced multiphoton ionization. The photofragment action spectra revealed multiple peak structures in both overtone regions, attributed to couplings of the C-H stretches and to methyl stretch-deformation Fermi resonances. The cooling of the samples afforded narrowing of-the peaks, relative to room temperature photoacoustic spectra, due to the reduced rotational and vibrational congestion, and enabled observation of a new splitting in the high frequency peak of the second overtone. This splitting apparently resulted from a local resonance of the mixed stretch-deformation state with a close lying dark state. The time scales for vibrational energy redistribution in the local resonance and between the mixed stretch-deformations were evaluated. These time scales and the measured Cl*/Cl branching ratios were compared to those of other hydrohalocarbon compounds. The Cl*/Cl ratio,was also compared to that of the nearly isoenergetic vibrationless ground state 193 nm photodissociation and found to. be different, demonstrating the effect of vibrational pre-excitation on the photodissociation dynamics.