A synthetic method for the end-functionalization of vinylidene fluoride oligomers (OVDF) via a radical reaction be-tween terminal olefins and OVDF-I is described. The method shows a wide substrate scope and excellent conversions, and permits the preparation of different disc-shaped cores such as benzene-1,3,5-tricarboxamides (BTAs), perylenes bisimide (PBI) and phthalocyanines (Pc) bearing three to eight ferroelectric oligomers at their periphery. The for-mation, purity, OVDF conformation, and morphology of the final adducts has been assessed by a combination of tech-niques, such as NMR, size exclusion chromatography, (SEC), differential scanning calorimetry (DSC), polarized optical microscopy (POM) and atomic force microscopy (AFM). Finally, PBI-OVDF and Pc-OVDF materials show ferroelec-tric hysteresis behavior together with high remnant polarizations, with values of as high as Pr ~ 37 mC/m2 for Pc-OVDF. This work demonstrates the potential of preparing a new set of ferroelectric materials by simply attaching OVDF oligomers to different small molecules. The use of carefully chosen small molecules paves the way to new func-tional materials in which ferroelectricity and electrical conductivity or light-harvesting properties coexist in a single compound.