The evaporation of sessile droplets placed on polymer surfaces was studied by microscopic observation of the changes in shape of aqueous solution droplets in which the alkyl lengths and the initial concentrations of sodium n-alkylates were varied. Although the initial contact angles of the droplets were not significantly different, the evaporation process varied significantly with the alkyl length of the sodium n-alkylate employed. For the sodium dodecanoate (C 12), showing the highest surface activity, the concentration was found to have a significant effect on the evaporation process of the droplets. In the evaporation of water droplets, variations in the three distinct stages were caused by the different concentration of solutes distributed near or at the air/water interface. It is revealed that the concentration of droplet solute near the air/water interface requires not only solvent evaporation but also some affinity of the solute for the interface. The initial C 12 concentration-dependence of the evaporation of C 12 solution droplets is discussed with particular emphasis on the sudden spreading or sudden contraction of the contact area near the end of evaporation. It is suggested that the cluster formation by C 12 molecules at the air/liquid interface during the evaporation causes Marangoni instability in an evaporating droplet, and the clusters are expected to move dynamically, depending on the droplet concentration of C 12, from the droplet center to the contact line and vice versa, showing Marangoni flow along the air/water interface.