AbstractThe aim of these investigations was the development of stationary phases for GPC compatible with fluorinated solvents. The properties of crosslinked copolymers of 4‐(2‐heptafluoropropoxy‐1, 2,2‐trifluoroethoxy)styrene (1) were investigated in dependence of the mode of synthesis. Divinylbenzene (DVB) was used as crosslinking agent. In the case of homogeneously crosslinked gels, 1 mol‐% of DVB results in a gel with an exclusion molecular weight of 2000. Heterogeneous crosslinking copolymerization of 1 with DVB in presence of inert diluents results in gels with exclusion limits from 5000 to 4000000 in dependence of the diluent composition. Characterization of the gels in GPC experiments was carried out with 2‐(1,2‐dibromotrifluoroethoxy)‐1,1,2,3,3,3‐hexafluoro‐1‐(perfluoropropoxy)propane (PPVE2Br2), hexafluorobenzene, 1,1,2‐trichlorotrifluoroethane (FrigenR113) and trifluoromethylbenzene as eluents.