Vitamins play important roles in our organism and are often marketed in the form of medicines. Several studies propose different methods for the determination of these substances in pharmaceutical samples. However, such papers often make use of expensive and complex methods, either in time or cost. From this observation, we tried to develop a simultaneous determination of vitamins with electroanalytical techniques and simple mathematical treatment, in order to make possible this analysis with a quick and cost-effective method, which is the objective of this study. With the methodology developed we obtained 99.9 % recovery for the potentiometric titration and 101.2 % recovery for the conductometric titration. The results were 104.7 mg mL-1 for thiamine and 97.0 mg mL-1 for pyridoxine, values similar to those described (100 mg mL-1) in drug leaflet of the formulation used as real sample. We can conclude that the proposed method is effective for its intended purpose.