Characterization techniques and results of polymer and inorganic thin films using Scanning Probe Microscopy (SPM) were presented. In view of principle, equipment and operation of SPM sample preparation, and surface morphologies of fiber, powder, and thin film were discussed. Techniques of image processing, analysis, and export were described in detail. In view of application, polypyrrole (PPy) films formed on alumina, mica, and graphite by admicellar polymerization showed, using SPM, a film thickness of tens of nm or a few nm under conditions of depleting adsolubilization. Wrinkling of thick PPy films (>100 nm), mostly prepared in the absence of surfactant, was observed on mica and interpreted as the overcoming of film-substrate adhesion by increased cohesion of the film during its growth. Droplets of an InSb alloy deposited on Si(100) using molecular beam epitaxy (MBE) were found to possess nicks on the surface which were interpreted as the volume change upon solidification. The calculated volume change from AFM images was 2.2% which corresponded to a 13% Sb in the alloy and agreed well with the value (16%) obtained from EDAX analysis. Effects of annealing on CaF2 thin films deposited on Si(100) were examined by SPM and the results showed that the crystalline CaF2 flattened and widened after annealing and that undesired polycrystals within the film promoted the formation of amorphous CaF2.