Evaporation and sliding behaviors of water droplets were investigated on smooth and rough fluoroalkylsilane coatings. The rough coating possesses nanoscale roughness and chemical heterogeneity on its surface. Evaporation behaviors for these two coatings differed when nanoliter-scale droplets were used, although they were nearly identical for microliter-scale droplets. The droplets on the smooth coating exhibit greater sliding acceleration and a larger slipping velocity ratio than those on the rough coating. Both the evaporation behavior of nanoliter-scale droplets and sliding velocity of microliter-scale droplets were affected by nanoscale surface heterogeneity. They are indicators for highly homogeneous smooth silane coatings.