This study investigates the solvation effect on the decarboxylation of o-phthalic acid using quantum calculations with a continuum solvation model with varying dielectric constants. Two mechanisms were considered: with and without a catalytic water molecule. The latter had a lower reaction barrier. Increasing the dielectric constant facilitates the hydrogen transfer but impedes C–C bond breaking in both mechanisms. The change in the free energies due to solvation of the transition state is generally greater than the reactant. The reaction barrier predominantly increased with the dielectric constant in both mechanisms. The Kirkwood slope estimated by plotting estimated rate constants against the Kirkwood polarity parameter, (ε−1)/(2ε+1), was close to the experimental value (only for the assisted mechanism). The simulations indicate that the solvation effect on the decarboxylation rate can be elucidated by considering the effect of dielectric constant of supercritical water.