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In this study, we introduced Ph-sensitive carboxymethyl poly (L-histidine) (CM-PLH) and Poly (β-amino ester) (PbAE) as functional biomaterials to form CM-PLH/PbAE/DNA ternary complexes system based on electrostatically for gene transfection in B16-F10 melanoma. METHODS and RESULTS The complexes kept good condensation capacity and low toxicity even provided a higher transfection efficiency than the binary complexes (PbAE/DNA) and transfected up to (57.1±2.10) % in B16-F10 in vitro. The ternary complexes significantly enhanced endosomal escape which was proved by the result that visualized under Fluorescence Confocal Microscopy (FCM). The in vivo gene transfection confirmed that the ternary complexes shown 4 fold higher luciferase expression in B16-F10 tumor than the binary complexes. CONCLUSION Consequently, CM-PLH/PbAE/DNA ternary complexes system exhibited significant improvements in transfection efficiencies in comparison with non-coated PbAE/DNA both in vitro and in vivo, highlighting their functional prospect.