Herein, it is demonstrated that star pseudopolyrotaxanes (star-pPRs) obtained from the inclusion complexation of -cyclodextrin (CD) and four-branched star poly(epsilon-caprolactone) (star-PCL) organize into nanoplatelets in dimethyl sulfoxide at 35 degrees C. This peculiar property, not observed for linear pseudopolyrotaxanes, allows the processing of star-pPRs while preserving their supramolecular assembly. Thus, original PCL:star-pPR core:shell nanofibers are elaborated by coaxial electrospinning. The star-pPR shell ensures the presence of available CD hydroxyl functions on the fiber surface allowing its postfunctionalization. As proof of concept, fluorescein isothiocyanate is grafted. Moreover, the morphology of the fibers is maintained due to the star-pPR shell that acts as a shield, preventing the fiber dissolution during chemical modification. The proposed strategy is simple and avoids the synthesis of polyrotaxanes, i.e., pPR end-capping to prevent the CD dethreading. As PCL is widely used for biomedical applications, this strategy paves the way for simple functionalization with any bioactive molecules.