Physicochemical and electrochemical properties of hydroxyphenyl boronic acids(HPBAs) and their use in fluoride determinations were investigated. HPBAs were electropolymerized at pH 1.0-11.0 in 40-60 %(v/v) methanol-buffer. Differential pulse voltammetry(DPV) determinations of fluoride (with 1.0 × 10 À 5 -1.0 × 10 À 4 M linearity based on potential shift) using poly(HPBAs) glassy carbon electrodes(GCEs) have À 45.49 to + 34.40 % error range. Significance of raw DPV data for chemometric discrimination was investigated by principle component analysis. This is the first demonstration of fluoride determination with poly(HPBAs)GCEs and chemometric discrimination of pharmaceutical formulations so far. Due to the lack of experimental data in literature, current findings will make a contribution to literature.