We characterize the structural and electronic changes during the photoinduced enol-keto tautomerization of 2-(2'-hydroxyphenyl)-benzothiazole (HBT) in a nonpolar solvent (tetrachloroethene). We quantify the redistribution of electronic charge and intramolecular proton translocation in real time by combining UV-pump/IR-probe spectroscopy and quantum chemical modeling. We find that the photophysics of this prototypical molecule involves proton coupled electron transfer (PCET), from the hydroxyphenyl to the benzothiazole rings, resulting from excited state intramolecular proton transfer (ESIPT) coupled to electron transfer through the conjugated double bond linking the two rings. The combination of polarization-resolved mid-infrared spectroscopy of marker modes and time-dependent density functional theory (TD-DFT) provides key insights into the transient structures of the molecular chromophore during ultrafast isomerization dynamics.