The molecular conformation and the phase structure of syndiotactic polypropylene gel were studied by infra-red and solid-state high resolution C-13 n.m.r. spectroscopies. It was found that the trans-trans-gauche-gauche molecular conformation, that is most energetically stable in the bulk crystalline state of this polymer, is also formed in the gel. However, the methylene resonance lines of the gel observed in solid-state C-13 n.m.r. spectrum are somewhat different from that of the bulk crystal. The origin of this difference is attributed to a difference in the intermolecular interaction. The investigation of the phase structure revealed that the gel generally comprises three phases; the crystalline phase, noncrystalline amorphous phase, and crystalline-amorphous interphase in a similar manner to the bulk crystals. About 64% of solvent molecules in the gel are incorporated in the crystalline-amorphous interphase as bound solvent and another 34% are in the amorphous phase as free solvent.