This article presents a study of the excited state relaxation dynamics of N-salicylidene-o-aminophenol (SOAP) in ethanol solution. Femtosecond transient absorption (TA) spectroscopy and theoretical calculations are used in combination to establish the mechanism of the excited state relaxation and type of molecular species involved in the accompanying phototransformations. TA spectra show that upon photoexcitation two SOAP tautomers (E-enol and Z-keto) interconvert by ESIPT. The molecule can subsequently isomerize to the E-keto form of SOAP. An intriguing observation is that the TA spectra of this compound in ethanol show modulations of the signal at the stimulated emission spectral range. It is found that these modulations are due to the coherence of the excited ensemble of molecules whose evolution over time represents a moving wave packet. After Fourier transform of the modulations, two characteristic frequencies are identified. These frequencies refer to the corresponding vibrational modes of the excited state and their nature is elucidated by DFT quantum chemical calculations. The obtained experimental and theoretical data reveal the nature of the vibronic coupling between the ground and excited state and the type of molecular vibrations involved in the molecular dynamics along the potential surface of the first excited state at the initial moment right after excitation. These vibrations characterize the starting point in the excited state dynamics of the molecule toward Z–E isomerization of the keto form of SOAP. This study provides a comprehensive picture of the dynamic processes taking place upon photoexcitation of the compound, which might enable control over the various relaxation channels.