In the present work, an alternative method for trans fatty acids (TFA) analysis with direct UV detection using capillary zone electrophoresis (CZE-UV) is proposed. The background electrolyte used consisted of 12.0 mmol L−1 of tetraborate buffer, 12.0 mmol L−1 of Brij 35, 33% methanol and 17% acetonitrile. Trans fatty acids in different samples such as butter toffee, cake mix, stuffed wafers, chocolate and a mix for Brazilian cheese bread were successfully quantified within an analysis time of 13 min, taking into account the statistical approach based on response factor calculation using C19:1 (nonadecaenoic acid) as internal standard. The statistical comparison between CZE-UV and the classical GC method for the analyzed samples did not present significant differences within the 95% confidence interval.