The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicylideneiminato)oxovanadium(IV) complex [VO(Salen)] as well as its behavior in relation to the oxidation of pyridoxine (Vitamin B6) are described. The electrochemical behavior of the modified electrode and the electrooxidation of pyridoxine were investigated using cyclic voltammetry. The best voltammetric response was obtained for an electrode composition of 15% (m/m) [VO(Salen)] in the paste, KCl solution of pH 5.5–8.0 and scan rate of 25 mV s−1. A sensitive linear voltammetric response for pyridoxine was obtained in the concentration range of 4.5×10−4 to 3.3×10−3 mol l−1 with a slope of 42.5 μA mmol−1 l, and a detection limit (3σ/slope) of 3.7×10−5 mol l−1 using linear sweep voltammetry. Among several compounds tested only Vitamin B1 seems to interfere in the analyte signal. The concentrations of pyridoxine in pharmaceutical formulations using the proposed electrode and an official spectrophotometric method based in the reaction with N,N-diethyl-p-phenylenediamine are in agreement at the 95% confidence level and within an acceptable range of error.