Poly(methyl methacrylate) (PMMA) is one of the most important polymers for application as a dielectric layer in organic electronics, e.g. in organic field-effect transistors. The key to improve the transistor performance is the optimization of the interface between the semiconductor and the dielectric layer. Here, the surface order in thin films of PMMA copolymers with self-organized, semifluorinated (sf) building blocks, and crosslinkable units in single layers and double layers with poly(3-hexylthiophene-2,5-diyl) (P3HT) is investigated. The chemistry of the sf copolymers is systematically varied and the influence on the self-organization in bulk and thin films is examined by a combination of scattering methods. The length of the semifluorinated side chains mainly determines the degree and type of order both in bulk as well as in thin films.