Polymeric thin films represent an emerging industrial area driven by their enormous technological and commercial potential in interdisciplinary sectors such as chemistry, material science, engineering, and physics. The large selection in terms of materials/composites and the wide range of technological solutions that could be used for their fabrication could create confusion for the final user requiring a quantitative characterization of their properties. This analysis could be even more complex in the case of functionalized polymeric films such as the samples reported in this work. Here we present how thin polymer films can be wholly characterized by applying a multiplicity of optical methods. Films were realized by a special liquid one-step process. Moreover, such polymer films were functionalized here for the first time by mesoporous silica nanoparticles. The nanoparticles were added to a polymeric matrix. We show that a full characterization was achieved by employing three different microscope techniques, i.e., scanning electron microscope, digital holography (DH), and space-time DH. Exploiting such a multimodal methodology can be of great benefit for characterizing the functionalized polymeric thin films. In fact, multiple characterization in different conditions was possible. The results reported in terms of morphological information, thickness distribution, three-dimensional (3D) mapping, large field of view, high magnification, and super resolution of the zoomed area offer a good solution for testing materials and obtaining a quantitative characterization and whole inspection in the case of complex polymeric samples.