Vitamin D and its association with cardiovascular disease (CVD) are currently a topic of investigation. The objective of this study was to explore the association between vitamin D status (serum 25-hydroxyvitamin D (25(OH)D)) and a cardiometabolic risk score (CMRS) derived from markers of cardiac autonomic nervous system activity, vascular dynamics, and body composition, using an innovative non-invasive technology. We found that individuals who were vitamin D sufficient ((25(OH)D) ≥ 30 ng/ml, n = 51), compared to those who were vitamin D insufficient (<30 ng/ml, n = 44), had significantly higher heart rate variability (as measured by time and frequency domain variables) and lower photoplethysmography analysis markers and CMRS. These outcomes show that vitamin D insufficient subjects had reduced cardio protective parasympathetic nervous system activity, increased endothelial dysfunction, and hence were at greater cardiometabolic risk, implying vitamin D may play a meaningful role in CVD.