Hypothesis: Supramolecular nanostructures via small molecule self-assembly hold great promise for controlled delivery of hydrophobic anticancer drugs. Particularly, taxol has recently been discovered to possess excellent self-assembly property, which may provide new opportunities to develop a new class of functional supramolecular nanomaterials for drug delivery application. Experiments: A cell penetrating peptide (CPP)-taxol conjugate (Taxol-CPP) was designed and synthesized. The self-assembling property of Taxol-CPP was investigated and the resultant nanomaterials were well characterized. Subsequently, the cytotoxicity of the Taxol-CPP after self-assembly against HepG2 cancer cells was evaluated. Findings: It is found that the Taxol-CPP possesses a high drug loading of 26.4% in each molecule, which is able to self-assemble into supramolecular nanospheres. By taking advantages of the self-assembly ability of taxol, Taxol-CPP supramolecular nanospheres with a mean size of around 130 nm can be obtained, composed of only the functional peptide (CPP) and the drug (taxol). Furthermore, we have demonstrated that the Taxol-CPP nanospheres do not compromise the taxol's potency, which can also be utilized as the carriers for co-delivery of another anticancer drug (doxorubicin). (C) 2015 Elsevier Inc. All rights reserved.