Two novel families of dimethacrylate-based thermoset resins containing oligo(tetrafluoroethene) segments with n=1, 2, 3 tetrafluoroethene units were prepared from dimethyl tetrafluorosuccinate, dimethyl octafluoroadipate and dimethyl dodecafluorosuberate. Methacrylate functionalities were determined using1H-NMR spectroscopy. Photocrosslinking by UV irradiation in the presence of photoinitiators affords amorphous networks. The influence of the oligo(tetrafluoroethene) segment length on glass transition temperatures, swelling, volume shrinkage and thermal degradation was investigated.