Compression form-fitted athletic wear (CFA) have been widely applied in special sports and various aerobic and fitness activities over recent years. Following the established 5Ps model in our previous study, an evaluation of basic psychophysiological measurements would assist in validating the practicality and effectiveness of these garments for athletic use. The present study was to examine the physiological property and wearing comfort of CFAs on athletes during intensive exercise. Heart rate (HR), blood pressure (BP), myocardial consumption (double product DP), blood oxygen levels (SpO2), skin and garment temperature (Tsk, Tg) over the athlete’s body were investigated. This study indicated that the application of CFAs maintained the body in the normal SpO2 range, and produced lower DP and HR compared to those in control condition. The application of CFAs resulted in a decrease on Tsk, which allowed the body quickly to cool down thus avoiding heat stress buildup during and after intensive exercise. The CFAs made by the performance knits with lightweight, gradient compression design and moisture-thermoregulation function presented lower Tg and brought the athletes satisfied wearing comfort perception. This study builds up an understanding on the potential physiological benefits induced by CFAs on athlete’s body in intensive exercise performance.