The microscopic region near the triple line plays an important role in the heat and mass transfer of droplets, although the mechanisms of evaporation and internal flow remain unclear. This paper describes an experimental study of fluid flow and thin-film evolution near the triple line in sessile droplets of self-rewetting fluids, aqueous solutions of alcohols with the number of carbon atoms varying from 1 to 7, to analyze the influence of various factors on the mesoscale flows. The mechanism of internal flow for self-rewetting fluid droplets was different from that of conventional fluids, and hence, a novel expression of the in-plane average velocity was fitted for them. The temporal and spatial evolution of the thin-film thickness near the triple line during droplet evaporation was obtained by using a proposed subregion method, which was developed from an evanescent-wave-based multilayer nanoparticle image velocimetry technique. The self-rewetting fluids are conducive to increase the microscopic critical contact angle and the energy barrier of the contact line, which reduces the rate of thin-film thickness variation. The inhibited impact of self-rewetting fluids on evaporation increases gradually with an increasing number of carbon atoms.