In this work, we studied the valence tautomerism process on two different Co-dioxolene complexes by means of transient infrared spectroscopy (TRIR). The molecules investigated are ls-Co-III(Cat-N-BQ)-(Cat-N-SQ) (DQ(2)) and [ls-Co-III(tpy)(Cat-N-SQ)]PF6 (tpy), where Cat-NBQ = 2-(2-hydroxy-3,5-ditert-butylphenyl-imino)-4,6-ditert-butylcyclohexa-3,5-dienone, Cat-N-SQ is the dianionic radical analogue, and tpy = 2,2 '-6-2 ''-terpyridine. DFT calculations of the harmonic frequencies for the two complexes allow us to pinpoint the normal modes to be used as markers of the semiquinonate and benzoquinonate isomers. The photoinduced one-electron charge transfer process from the radical semiquinonate ligand to the metal center leads to a ls-Co-II(x)(Cat-N-BQ) electronic state (where x is the other ligand). Following this first step, an ultrafast ISC process (tau < 200 fs) takes places, yielding the benzoquinonate isomer (hs-Co-II(x)(Cat-N-BQ)). In the experiments, we employed different excitation wavelengths on resonance with different absorption bands of the two samples. Excitation in the ligand-to-metal charge transfer (LMCT) band at similar to 520 nm and in the semiquinonate band at similar to 1000 nm induces the valence tautomerism (VT) in both samples. From the time evolution of the TRIR spectra, we determine the time constants of the vibrational cooling in the tautomeric state (7-14 ps) and the ground state recovery times (similar to 350 ps for tpy and similar to 450 ps for DQ(2)). In contrast, when the pump frequency is set at 712 nm, on resonance with the benzoquinonate absorption band of the second active ligand of the DQ(2), no electron transfer takes place: the TRIR spectra basically show only ground state bleaching bands and no marker band of the tautomeric conversion shows up.