The ABA-type triblock-copolymers (BCPs) of polylactide (PLA) and poly(ethylene glycol) (PEG) were synthesized as axle components for rotaxane formation. It is known that α-cyclodextrin (CD) exists near the PEG moiety in pseudo-polyrotaxane (PPRX), and the PLA moiety can form a stereocomplex (SC), by mixing with L- and D-isomers. In this study, various CDs, including β-CD and γ-CD, were used as wheel components, and effects of CD structures on both PPRX and SC formations were studied. The solubility of CDs is influenced to form the PPRX, resulting in differing numbers of CDs in the axle. PPRX structures were investigated by 1H NMR, NOESY, and DOSY, and SC structures were investigated by FT-IR and XRD. Their thermal properties were also evaluated by DSC and TGA, to consider the physical properties of the simultaneous formation of PPRX and SC. This study gave insight into the complicated host-guest and polymer-polymer interactions.