The protonation reaction of the carboxyl (-COOH) functional group fixed at the surface of polystyrene carboxylate (PSC) microspheres, with a radius of 457 ( 14 nm, dispersed in aqueous medium has been studied using the nonlinear optical method of second harmonic generation (SHG). We have demonstrated that the " (3) method," along with the use of the Gouy-Chapman model describing the surface potential, can be used to determine the pK a of carboxyl groups at the particle-liquid interface. A surface pK a of 5.4 ( 0.3 has been determined for the PSC colloidal particles, which corresponds to a decrease in the acidity; that is, K a is a factor of 4 smaller at the interface than that of long chain carboxyl acids in bulk aqueous solution.