Covalently grafted pyrene moieties onto the K-7[PW11O39]center dot 13H(2)O cluster (K-7-PW11) results in the formation of a new organic/inorganic hybrid with the molecular formula of (Bu4N)(4){(PW11O39)[O(Si(CH2)(3)NH-COOCH2C16H9)(2)]} (Py-PW11), which has been immobilized onto single-walled carbon nanotubes (SWNTs) homogeneously via pi-pi stacking and electrostatic interactions. The resulting SWNTs/Py-PW11 nanocomposite material exhibits excellent adsorption of human serum albumin (HSA), as evidenced by high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS) studies. This work paves a new pathway for the development of polyoxometalate (POM)-based biomaterials.