Poly-pseudo-rotaxanes CDs superset of D1 (CDs; cycloclextrins, 1; poly(delta-valerolactone) having single P-CD at the end of the polymer chain) initiate polymerization of delta-valerolactone (delta-VL) in the solid state when CDs (alpha-CD, ss-CD, and 2,6-di-O-m ethyl-ss-C D) are threaded onto the polymer chain. 1 without threaded CDs did not show any polymerization ability for delta-VL. An adamantano molecule (Ad) inhibited the polymerization ability of CDs superset of 1 for delta-VL, indicating that ss-CD at the end of CDs superset of 1 could not bind delta-VL because the P-CD cavity was occupied by Ad. It should be noted that the insertion reaction and the polymerization took place inside the ss-CD cavity at the end of CDs superset of 1 and that the formation of polypseudo-rotaxane is necessary for the initiation of delta-VL. The structures of ss-CD superset of I and 1 were characterized by powder X-ray diffraction measurements and solid-state NMR spectroscopies. The polymer chain of ss-CD superset of 1 was found to elongate in the solid state, whereas the polymer chain of 1 formed a random coil conformation. 1 was deactivated for the polymerization by blocking the active cavity of ss-CD with the polymer chain. CDs threaded onto 1 are immune to the initiation of delta-VL directly but have an essential role to fold the polymer chain in a proper way as an artificial chaperone.