The miscibility of blends of single [60]fullerene (C-60)-end-capped poly(ethylene oxide) (FPEO) or double C-60-end-capped poly(ethylene oxide) (FPEOF) with poly(vinyl chloride) (PVC) has been studied. Similar to poly(ethylene oxide) (PEO), both FPEO and FPEOF are also miscible with PVC over the entire composition range. X-ray photoelectron spectroscopy showed the development of a new low-binding-energy C12p doublet and a new high-binding-energy O1s peak in FPEO/PVC blends. The results show that the miscibility between FPEO and PVC arises from hydrogen bonding interaction between the alpha -hydrogen of PVC and the ether oxygen of FPEO. From the melting point depression of PEO, FPEO or FPEOF in the blends, the Flory-Huggins interaction parameters were found to be -0.169, -0.142, -0.093 for PVC/PEO, PVC/FPEO and PVC/FPEOF, respectively, demonstrating that all the three blend systems are miscible in the melt. However, the incorporation of C-60 slightly impairs the interaction between PEO and PVC.