Boronic acid-based sensors for saccharides have been developed via biocatalysis. The self-doped copolymer of poly(aniline-co-3-aminobenzeneboronic acid) [poly(aniline-co-AB)], with various mole ratios of two components, was synthesized by oxidative enzymatic polymerization using a natural biocatalyst such as horseradish peroxidase together with an anionic polyelectrolyte template (sulfonated polystyrene) under mild conditions (pH 4.5). Poly(aniline-co-AB), having an aniline boronic acid-to-aniline ratio of 1:2 on average, gave rise to a green doped polymer with absorption maxima at 745 nm. The potentiometric detection of saccharides using poly(aniline-co-AB) is presented. Characteristics of both transient and steady-state response associated with the complex formation of poly(aniline-co-AB) with various saccharides were monitored by UV-vis spectroscopy and cyclic voltammetry (CV). The results obtained from UV-vis spectroscopy and CV show that the sensitivity of enzymatically synthesized water-soluble poly(aniline-co-AB) for various saccharides was improved significantly compared to the chemically synthesized counterpart. A possible mechanism for the sensitive detection of sugar molecules by boronic acid is proposed on the basis of UV-vis and IR spectrophotometry, and four-point probe conductivity measurements.