Gels of syndiotactic polystyrene with different solvents have been compared to clathrates. Wide-angle X-ray diffraction results using toluene (good solvent for sPS) and decalin (relatively poor solvent for sPS) show that the structure of the crystalline junctions of the gels is similar to that of the clathrate δ-phase. A difference can be found in the width of the (010) reflection, which is, relative to the width of the (2̄10) reflection, much broader for the gel than for the clathrate. This is caused by the difference in mechanism involved for crystal formation in gels and clathrates. Experiments performed on quenched samples of syndiotactic polystyrene with the monomer benzyl methacrylate show that also for this gel the structure of the crystalline part is similar to that of the clathrate phase. This means that solvent is present in both the crystalline and the amorphous part of the gel. By solid-state NMR studies, a clear difference in mobility of solvent molecules in the crystalline and amorphous parts of the gel has been observed.