In an electrolytic cell with a proton exchange membrane, nicotinic acid was synthesized at the PbO2 anode. The relationship between the current density and the potential at different concentrations of 3-picoline and sulfuric acid as well as at different temperatures was studied with polarization curves. The effects of the concentrations of sulfuric acid and 3-picoline, the anode potential and the reaction temperature on the selectivity and the current efficiency were explored. The optimum conditions were determined by orthogonal experiments. Under optimum conditions the selectivity and the current efficiency for the synthesis of nicotinic acid might reach 89% and 65%, respectively. The concentrations of 3-picoline and nicotinic acid were analyzed with high performance liquid chromatography and the product was characterized with elemental analysis, chromatography-mass spectrometry and IR spectrometry.