Acute mental stress (MS) induces a transient increase in arterial stiffness. We verified whether a single bout of bench step (BS) exercise for 3 minutes counteracts acute MS-induced arterial stiffening. Fifteen healthy young men (mean age, 21.7 ± 0.3 years) underwent two experimental trials: rest (RE) and exercise (EX) trials. Following a 5-minute MS task, the participants in the RE trial rested on a chair for 3 minutes (from 10 to 13 minutes after task cessation), whereas those in the EX trial performed the BS exercise for the same duration. The heart-brachial pulse wave velocity (PWV) (hbPWV), brachial-ankle PWV (baPWV), heart-ankle PWV (haPWV), and the cardio-ankle vascular index (CAVI) were measured at baseline and at 5 and 30 minutes after the task. In both trials, significant increases in hbPWV, haPWV, and CAVI occurred at 5 minutes after the task; these elevations persisted until 30 minutes after the task in the RE trial, but significantly decreased to baseline levels in the EX trial. baPWV was significantly elevated at 30 minutes after the task in the RE trial, but not in the EX trial. This study reveals that a 3-minute BS exercise offsets acute MS-induced arterial stiffening.