A bis-phenanthroline [2]catenane copper complex, consisting of one olefinic macrocycle and one nonolefinic macrocycle, underwent an entropy-driven ring-opening olefin metathesis polymerization (ROMP) to provide a polypseudorotaxane. The polymerization featured an average degree of polymerization of ca. 63 wherein the polymer was effectively saturated with threaded macrocycles. Removal of the copper led to near complete release of the macrocycles from the polymer backbone.