The diffusion-controlled evaporation of small circular volatile liquid films from solid surfaces was monitored by employing video microscopy from a plan view and then applying digital image analysis techniques. The decrease of the liquid-solid contact area of these films during the last stages of the evaporation was found to be linear with time. This paper presents experimental results of four organic liquid films (n-nonane, n-octane, toluene, n-butanol) on three substrates poly(methyl methacrylate), poly(ethylene terephthalate) (Mylar), and glass. The linear decreases of the surface areas of hanging drops from a polypropylene fiber for the same liquids were also monitored using both plan and side view video cameras for comparison. Analyses of optically recorded liquid film and drop shapes were carried out and a diffusion model depending on the presence or absence of the substrate was developed. By combining the experimental area decrease of a spherical drop due to the diffusion-controlled evaporation with that of a small spherical cap shaped liquid film resting on a solid surface, it is possible to calculate the small contact angles (less than 10degrees) of the wetting thick liquid films on solids. The relationship between film evaporation rate and the solid-liquid interfacial interactions is also discussed.