This work was developed an analytical methodology for determination of selenium in samples of vitaminic complex using the square wave voltammetry (SWV). The analysis were performed with a copper electrode modified with bismuth film deposited by applying a potential of -400 mV for 60 seconds in a solution containing HCl 0.2 mol L-1, 20 g L-1 and 500 µg L-1 of Bi(III). The variables: time and conditioning potential were optimized by SWV for the formation of the bismuth film, after that, the variables that affect the analytical sensitivity for the reduction of Se (IV): frequency, increment and high of pulse were also optimized. The linearity of the method ranged from 90 – 1180 µg L-1. Limit of detection of 26,4 µg L-1, quantification limit of 87,9 µg L-1. Analytical frequency of 30 samples/hour. The method showed excellent precision, calculated as the relative standard deviation (RSD%) (n = 5) using spiked solution of 150 µg L-1. The concentration of selenium found in the sample of the vitaminic complex was 24 µg/tablet. A study of recovery was performed resulting in 92%.