The primary objective of this study was to determine the effects of vitamin D levels on peripheral pulse wave velocity (pPWV) following acute maximal exercise in healthy young adults. Fifty male healthy adults from National Chung Cheng University participated in the study. Participants were divided into the 25-hydroxyvitamin D (25(OH)D) sufficiency group (n = 28, 25(OH)D ≥ 50 nmol/L) and deficiency group (n = 22, 25(OH)D < 50 nmol/L). The acute maximal exercise was performed using an incremental cycling test to exhaustion. Additionally, the pPWV and blood pressure were obtained at rest and 0, 15, 30, 45, 60 min after acute maximal exercise. The results show that 25(OH)D deficiency group had higher pPWV at post-exercise (5.34 ± 0.71 vs. 4.79 ± 0.81 m/s, p < 0.05), post-exercise 15 min (5.13 ± 0.53 vs. 4.48 ± 0.66 m/s, p < 0.05) and post-exercise 30 min (5.26 ± 0.84 vs. 4.78 ± 0.50 m/s, p < 0.05) than the sufficiency group. Furthermore, there was a significant inverse correlation between 25(OH)D levels and pPWV following acute maximal exercise. Our study demonstrated that low vitamin D status relates to the poor response of pPWV following maximal exercise in healthy young men. Vitamin D deficiency may increase the risk of incident cardiovascular events after acute exhaustive exercise, even in healthy and active adults.