Thermophysiological responses and clothing microclimate under the influences of different underwear materials were compared during walking and recovery in the cold. Two kinds of underwear were used: two layers of cotton underwear with two-piece long-sleeved shirt and long-legged trousers (C), two layers of polypropylene underwear with two-piece long-sleeved shirt and long-legged trousers (P). In addition, the subject put on a two-piece ski suit of 100% polyester including 100% polyester padding. Seven adult females served as subjects in this study. The test was done in a climatic chamber at an ambient air temperature of 2°C, a relative humidity of 65% and an air velocity of 0.14 m·s^-1. The subject walked on a motor-driven treadmill with a 6 km/h speed for 30 min followed by 60 min recovery. Rectal temperature, skin temperatures, clothing microclimate (temperature, humidity), metabolic heat production and heart rate were measured. Furthermore, subjective ratings on thermal sensation, sweating/shivering sensation, clothing wettedness sensation and skin wettedness sensation for whole body were asked. The major findings are summarized as follows: 1) Mean skin temperature was not significantly different during walking, but it was significantly higher in P than in C during the recovery. 2) The absolute humidity of innermost layer and outermost layer were not significantly different during walking, but it was significantly higher in P than in C during the recovery. 3) Clothing microclimate temperature of innermost was not significantly different during the first half of walking, but it was significantly higher in C than in P during the second half of walking and significantly lower in C than in P during the recovery. Clothing microclimate temperature of outermost was not significantly different during walking, but it was significantly higher in P than in C during the recovery. 4) Metabolic heat production for the last 10 min during recovery tended to be higher in P. 5) The degree of skin wettedness sensation and clothing wettedness sensation for whole body was significantly higher in P during walking and recovery. Thus, it was concluded that two kinds of underwear with different properties to moisture could influence, not only clothing microclimate, but also physiological parameters like skin temperatures and metabolic heat production in the cold differently.