Urban heat islands (UHI) are growing in size and intensity, which is partly attributable to the large amount of anthropogenic waste heat. Moreover, heat emitted from building exterior walls accounts for a large portion of the total anthropogenic waste heat. Thus, strategies and technologies for preventing the emission of heat from building exterior walls are being pursued by researchers worldwide. Amongst these technologies, the potential of use of retro-reflective (RR) materials instead of diffuse highly reflective (HR) materials applied to building envelopes for UHI mitigation is being studied widely. However, RR materials haven’t been applied to building envelopes in practice due to their unproven weather resistance. In order to develop RR materials with high weather resistance for application to building envelopes, two types of micro glass beads with different refractive indices (1.5, 1.9) and five different colors of base layers were evaluated in this study. Their RR performance was measured by optical experiment and compared to two types of RR sheets commercially available in Japan. The results showed that the glass bead RR samples with a refractive index of 1.9 had much higher retro-reflectivity (better RR capacity) compared to those with a refractive index of 1.5.