Currently, atomic force microscopy is the preferred technique to determine roughness on membrane surfaces. In this paper, a new method to measure surface roughness is presented using a 3D laser scanning confocal microscope for high-resolution topographic analysis and is compared to conventional SEM. For this study, the surfaces of eight samples based on a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) host polymer with different liquid interpenetrating components were analyzed. Polymethylhydrosiloxane, triethylene glycolallylmethyether, (3,3,3-trifluoropropyl) methylcyclotrisiloxane (D-3-C2H4CF3), polysiloxane-comb-propyloxymethoxytriglycol (PSx), poly-siloxane-comb-propyl-3,3,3-trifluoro (PSx-C2H4CF3), poly [bis(2-(2-methoxyethoxy) ethoxy) phosphazene, or poly [bis(trifluoro) ethoxy] phosphazene was chosen as interpenetrating compound to investigate the impact of comb and double-comb-structured polymer backbones, as well as their dipolar or fluorous residues on the PVDF-HFP-miscibility. Different phases of the constituting ingredients were identified via their thermal properties determined by DSC. Additionally, the COSMO-RS method supported the experimental results, and with regard to computed sigma-profiles, new modified structures for polysiloxane and polyphosphazene synthesis were suggested.