Star-shaped porphyrin-cored poly(-caprolactone)(SPPCL) was synthesized using a tetrahydroxyethyl-terminated porphyrin as a core initiator and stannous octoate as a catalyst in bulk at 120℃. The molecular weight of assynthesized polymer could be adjusted linearly by controlling the molar ratio of caprolactone to porphyrin core initiator, and the molecular weight distribution was reasonably narrow. Supramolecular polypseudorotaxanes were prepared by inclusion complexation of SPPCL with R-cyclodextrin (R-CD) and thoroughly characterized by means of FT-IR, 1H NMR, 13C CP/MAS NMR, DSC, TGA, and WAXD. The results demonstrated that the porphyrincored polypseudorotaxanes formed through R-CD molecules threading onto the branch chains of star-shaped SPPCL polymers, and they had a channel-type crystalline structure. Meanwhile, the original crystallization of SPPCL polymers within the polypseudorotaxanes was completely suppressed in the R-CD cavities. Moreover, inclusion complexation between SPPCL and R-CD enhanced the thermal stability of both the guest SPPCL polymers and the host R-CD. Furthermore, both the SPPCL polymers and the polypseudorotaxanes showed similar fluorescent and UV-vis spectra compared with porphyrin core initiator. Consequently, this will not only provide potentially porphyrin-cored poly(-caprolactone) and its polypseudorotaxanes for photodynamic therapy but also improve the compatibility between poly(-caprolactone) and peptide drugs for drug delivery.