A novel approach for the potentiometric detection of saccharides using poly(aniline boronic acid) is presented. A model is described in which the electrochemical potential is sensitive to the change in the pK(a) of the conducting polymer as a result of boronic acid-diol complexation. In this system, boronic acid complexation is the mode of transduction and it is manifested as changes in the electrochemical potential of the polymer with remarkable selectivity. Characteristics of both transient and steady-state response associated with the complexation are discussed. The presence of Nafion and fluoride during the electrochemical polymerization of 3-aminophenylboronic acid are shown to impact the sensitivity and the stability of the electrode response. The sensor sensitivity is improved significantly by increasing the concentration of sodium fluoride during the polymerization. Finally, the nature of the selectivity of the boronic acid-diol reaction under these conditions is explored by using molecular orbital calculations.