Cyclic poly(5-hydroxy-1-cyclooctene) (PACOE) was synthesized by ring-expansion metathesis polymerization (REMP), and thiol-ene chemistry was used to cross-link the internal double bonds in the PACOE backbone. This created a novel network material (gels formed from cyclic polymers) with unique structural units, where the cyclic PACOE main chains, which serve as secondary topological cross-linkages, were connected by primary intermolecular chemical cross-linkages. The resulting properties were notably different from those of traditional chemically cross-linked linear PACOE gels, whose gel fraction (GF) and modulus (G) increased while the swelling ratio (Q) decreased with increasing initial polymer concentration in the gel precursor solution (C-0). For the gels formed from cyclic polymers, however, the GF, Q and G all simultaneously increased as C-0 increased at the higher range. Furthermore, at the same preparation state (same C-0), the swelling ability and the maximum strain at break of the gels formed from cyclic polymers were always greater than those of the gels formed from linear polymers, and these differences became more pronounced as C-0 increased.