First-principle-based electronic structure calculations were carried out on microhydrated trifluoroacetic acid clusters (CF₃COOH, tfa) to understand its molecular level interaction with water and subsequent ionic dissociation to form CF₃COO⁻ ion. From severalgeometrical inputs, the global minimum energy structure of hydrated cluster, tfa·nH₂O (n = 1−7), was obtained adopting dispersion-corrected density functional, namely, ωB97X-D, and a set of correlated atomic basis function, aug-cc-pVDZ. It was predicted that tfa requires at least six H₂O molecules to dissociate. Energy parameters of these hydrated clusters were improved by applying MP2 as well as CCSD(T) methods. A linear variation was observed for calculated solvent stabilization energy profile with the number of solvent H₂O molecules present in the hydrated cluster. However, the calculated interaction energy profile showed the characteristic feature indicating the formation of contact ion-pair on the addition of six H₂O molecules to tfa. On the basis of energy decomposition analysis, it was observed that the major interaction between tfa and H₂O molecules was of electrostatic nature. On successive addition of water molecules, the electrostatic component of the interaction between solute and solvent molecules depicted a sudden increase when moving from penta- to hexahydrated cluster. This observed nature of energy profile coincided with the formation of hydronium ion in the case of hexahydrated cluster. The formation of H₃O⁺ was manifested in simulated IR spectra of tfa·6H₂O and tfa·7H₂O clusters. A large red shift in IR peak positions corresponding to O−H stretching of tfa was predicted on microhydration.