The major physiological adaptations that occur during heat acclimation (HA) are well documented. However, no studies have provided compelling evidence about the effect of HA on arterial elastic properties. The aim of this study was to examine the changes in large artery elasticity (LAE) and small artery elasticity (SAE) concomitant with HA and to determine the potential relationships among changes in arterial elasticity, baseline aerobic fitness level, and improvement in endurance capacity (EC). During 10-day HA, the subjects (n = 21) exercised daily on a treadmill for 110 min at an intensity of 55%-60% of peak oxygen uptake in a climatic chamber preset to 42 °C and 18% relative humidity. EC was tested in the heat before and after HA. Arterial elasticity was assessed by diastolic pulse wave analysis (HDI/Pulse Wave CR-2000) at baseline and after HA. Blood samples were drawn at baseline. After HA, there was a 17% increase in LAE (from 21.19 ± 4.72 mL·mm Hg(-1) × 10 to 24.77 ± 5.91 mL·mm Hg(-1) × 10, p < 0.05) and an 18% increase in SAE (from 9.32 ± 1.76 mL·mm Hg(-1) × 100 to 10.98 ± 1.75 mL·mm Hg(-1) × 100, p < 0.01). EC increased by 86% (from 88.62 ± 27.51 min to 161.95 ± 47.80 min, p < 0.001) as a result of HA. No significant associations were revealed between changes in arterial elasticity parameters and improvement in EC or baseline aerobic fitness level. We demonstrated, for the first time, that HA has a positive impact on the parameters of arterial elasticity. Further investigations are needed to determine the mechanisms underlying these changes and the potential relationships among arterial elasticity, aerobic fitness level, and EC.