Many important technologies depend on applications of organic thin films. The properties of surfaces and interfaces of film/substrate structures are of particular importance. It is becoming apparent that the atomic force microscope (AFM) has much to offer, especially when in situ non-destructive characterization is required. The ability of AFM to provide high resolution topographical images is well-developed. Recent studies have shown that force vs. distance (F–d) analysis can map at high spatial resolution mechanical properties of organic films, as well as those of the substrate. The same mode will also provide quantitative information about adhesive interactions. A formalism has been developed, based on a series combination of linearly compliant elements, from which film thickness and elastic moduli can be inferred from the detailed structure of F–d curves. The methodology is illustrated for the native lipid layer on wool fibre and for the multilayer structure of magnetic tapes.