Square wave voltammetric method was used to study the electrochemical properties of pyridoxine and determine it in pharmaceutical preparations using Cobalthexacyanoferrate modified carbon paste electrode. Various parameters such as pH of the buffer solution, electrode composition, pulse amplitude, step potential and frequency were investigated. The optimized parameter has been made at the electrode composition of 20% CoHCF, 55% graphite and 25% paraffin oil. The peak current depends linearly on the concentration of vitamin B6 from 5.0×10−6 M to 2.6×10−5 M with a correlation coefficient of r = 0.99997 (n = 8) and a standard deviation (S) of 0.005. The equation was found to be Ip (μA) =2.03277+0.10008C (μM) with the detection limit of 1.72 × 10−7 M. The developed voltammetric method was applied for the determination of Pyridoxine in vitamin B6 tablets and it yielded a good mean recovery.