The one-pot synthesis of a main chain-type polyrotaxane composed of axle molecules threaded through the macrocyclic units on the polymer main chain was achieved via the combination of cyclopolymerization and clipping procedures. The cyclopolymerization of an a, x-diethynyl monomer bearing an isophthalamide moiety (1), which clips onto an axle component bearing a pyridiniumdicarboxamide moiety (2 center dot Cl) through a chloride anion was carried out in chloroform with the monomer concentration of 0.06 mol L(-1) at 40 degrees C using [Rh(nbd)Cl](2)/Et(3)N as a catalyst to afford a gel-free polymer. The resulting polymer was assigned to the main chain-type polyrotaxane with a poly(phenylacetylene) backbone (poly-3 center dot Cl) based on size exclusion chromatography and (1)H NMR measurements. The diffusion-order two-dimensional NMR and circular dichroism spectra provided definitive proof of the rotaxaned architecture in the polymer. The mole fraction of the rotaxane unit in the total cyclic repeating unit was determined to be 26.3%. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 3184-3192, 2011