Solar reflective “cool pavements” have been proposed as a potential heat mitigation strategy for cities. However, previous research has not systematically investigated the extent to which cool pavements could reduce urban temperatures. In this study we investigated the climate impacts of widespread deployment of cool pavements in California cities. Using the Weather Research and Forecasting model, we simulated the current climate of California at 4 km spatial resolution. Comparing this simulation to 105 weather stations in California suggested an overall mean bias (model minus observation) of −0.30°C. Widespread pavement albedo increases of 0.1 and 0.4 in California cities were then simulated. Comparing temperature reductions for each scenario showed that the climate response to pavement albedo modification was nearly linear. Temperature reductions at 14:00 local standard time were found to be 0.32°C per 0.1 increase in grid cell average albedo. Temperature reductions were found to peak in the late morning and evening when (a) boundary layer heights were low and (b) solar irradiance (late morning) and heat accumulation in the pavement (evening) was high. Temperature reductions in summer were found to exceed those in winter, as expected. After scaling the results using realistic data-derived urban canyon morphologies and an off-line urban canyon albedo model, annual average surface air temperature reductions from increasing pavement albedo by 0.4 ranged from 0.18°C (Palm Springs) to 0.86°C (San Jose). The variation among cities was due to differences in baseline climate, size of the city, urban fraction, and urban morphology.