A simple, precise and reliable spectrophotometric method for the determination of pyridoxine hydrochloride (vitB6) and nicotinamide (vitB3) in pure form and pharmaceutical formulations has been described. The method is based on the reaction of studied vitamin with a mixture of potassium iodide and potassium iodate in aqueous medium at (250.5oC) to form yellow colored tri iodide ions (I3-). The reaction is followed spectrophotometrically by measuring the absorbance at 290, 335 and 288, 350 nm for vitB6 and vitB3 respectively. Beer's law was obeyed in the range of 0.5-20.0 μg mL-1 for all procedures. Molar absorptivities were found to be 1.49×104, 1.93×104 and 0.89×104, 1.25×104 L mol-1 cm-1, for determination of vitB6 and vitB3 at 290, 335 and 288, 350 nm respectively. The proposed method has been applied to determine the components in commercial forms with no interference from the excipients. A comparative study between the suggested procedures and the official methods showed no significant difference between the two methods.