Vibrational dynamics in different modes of (CF 3 ) 2 CCO molecule induced by resonant femtosecond IR excitation of the ν 1 mode is studied. Selective multiphoton excitation of this mode is observed up to the level v=7. Intramolecular vibrational redistribution (IVR) causes relaxation of the ν 1 mode with a time constant τ IVR =5ps. The ‘instantaneous’ (τ≪τ IVR ) transient absorbance ΔOD signal at nonresonant modes ν 2 , ν 3 , and ν 4 is revealed. Subsequent evolution of the ΔOD signal and the corresponding time constants are different for different modes, which we associate with different migration pathways of the vibrational energy.