The photodecarboxylation reaction of 2-(3-benzoylphenyl)propionate (ketoprofen anion, KP⁻) was studied in water and in 0.1 M phosphate buffer solutions in the pH range 5.7–11.0 by laser-induced optoacoustic spectroscopy (LIOAS, T range 9.5–31.6°C). Upon exciting KP⁻ with 355 nm laser pulses under anaerobic conditions, two components in the LIOAS signals with well-separated lifetimes were found (τ₁ < 20 ns; 250 < τ₂ < 500 ns) in the whole pH range, whereas a long-lived third component (4 < τ₃ < 10 μs) was only detected at pH ≤ 6.1. The heat and structural volume changes accompanying the first step did not depend on pH or on the presence of buffer. The carbanion resulting from prompt decarboxylation within the nanosecond pulse (<10 ns) drastically reduces its molar volume ([−18.9 ± 2.0] cm³/mol) with respect to KP⁻and its enthalpy content is (256 ± 10) kJ/mol. At acid pH (ca 6), a species is formed with a lifetime in the hundreds of ns. The enthalpy and structural volume change for this species with respect to KP⁻ are (181 ± 15) kJ/mol and ( 0.6 ± 2.0) cm³/mol, respectively. This species is most likely a neutral biradical formed by protonation of the decarboxylated carbanion, and decays to the final product 3-ethylbenzophenone in several μs. At basic pH (ca 11), direct formation of 3-ethylbenzophenone occurs in hundreds of ns involving a reaction with the solvent. The global decarboxylation reaction is endothermic ([45 ± 15] kJ/mol) and shows an expansion of ( 14.5 ± 0.5) cm³/mol with respect to KP⁻. At low pH, the presence of buffer strongly affects the magnitude of the structural volume changes associated with the intermolecular proton-transfer processes of the long-lived species due to reactions of the buffer anion with the decarboxylated ketoprofen anion.