The effects of reflectance of solar radiation have been well studied in terms of the paints used on paving and on building surfaces. However, there is insufficient information on reflectance in terms of clothing color, which is important for outdoor thermal comfort. Moreover, since the Fukushima Daiichi Nuclear Power Plant accident in March 2011, there has been an emphasis on the need to save on electricity use by limiting air-conditioning in summer. We observed surface temperatures of polo shirts of the same material and design but different colors; the shirts were hung in unshaded outdoor open space on the campus of NIES (National Institute for Environmental Studies), Tsukuba, Japan, on sunny days in August 2011. Color brightness is considered to represent the reflectance of visible light. In the early stage of this observation (morning), the order of the colors in terms of the observed surface temperatures was nearly exactly the reverse order of the color brightness values. Brightness is an important determinant of solar radiation albedo. The maximum difference between black and white was almost 20 °C and was greatest when the solar radiation was strong. Reflection performance in the near-infrared band is also an important determinant of surface temperature.