Patterned films of poly(styrene-co-maleic anhydride) copolymers were deposited by dip-coating from acetone solutions. A qualitative study of the film morphologies shows the formation of polymer spheres with smaller diameters at higher amounts of maleic anhydride (MA), and long-fibrous features at higher molecular weights. Upon heating, the films progressively re-assemble with short- and long-fibrous structures as a function of heating time and temperature. In parallel, the film morphologies are quantified by image processing and filtering techniques. The differential scanning calorimetry confirms the higher glass transition temperatures with increasing amount of MA. The analysis with Raman spectroscopy shows interactions between the molecules in solution and effects of ring-opening (hydrolysis) and ring-closure (formation of MA) during drying of the films. The water contact angles on the patterned films are within the hydrophilic range. They mainly correlate with the amount of MA moieties calculated from spectroscopy, while the roughness parameters have a minor effect. The variations in film patterns illustrate the self-assemble ability of the copolymers and confirm a heterogeneous molecular structure, as previously assumed.