We have recently developed a new method for synthesizing polyrotaxanes with a high covering ratio, rigidity, photoluminescence efficiency, and solubility in a variety of organic solvents through the polymerization of structurally defined rotaxane monomers. The rigid rodlike structure of the pi-conjugated core polymers in these polyrotaxanes is thought to facilitate the effective transport of charge carriers. Here we applied this method to the synthesis of a polyrotaxane having a poly(phenylene ethynylene) backbone by the Sonogashira copolymerization of a structurally defined rotaxane with a tinker molecule. According to time-resolved microwave conductivity and transient absorption spectroscopy measurements, the hole mobility along the pi-conjugated polymer chain of the polyrotaxane thus formed was extremely high and comparable to that in amorphous silicon.