Research suggests that sedentary behavior (SB) is negatively associated with cognitive outcomes. Interrupting prolonged sitting has been shown to improve cognitive functions, including executive functioning (EF), which is important for academic performance. No research has been conducted on the effect of standing on EF in VET students, who make up a large proportion of the adolescent population and who are known to sit more than other students of this age. In this study, we investigated the acute effects of reducing SB by short time standing on EF in vocational education and training (VET) students. In a randomized crossover study, 165 VET students were first taught for 15 min in seated position. After this, they performed while seated the Letter Memory Test for updating, and the Color Shape Test for shifting and inhibition. Students were randomly assigned to a sitting or standing condition. All students were taught again for 15 min and then took the same tests in the condition they were allocated to, respectively, standing or seated. After 1 week, the test procedure was repeated, in which students switched conditions. Mixed model analyses showed no significant effect of sitting or standing on updating, shifting, or inhibition. Also, no significant differences were found for the order of condition on updating, shifting, or inhibition. Our results suggest that 40 min of standing does not significantly influence EF among VET students.