Chemical coupling of maleated polyethylene (MAPE) copolymers at the interface in wood-fiber/high-density-polyethylene (HDPE) composites was investigated in this study. FTIR and ESCA analyses presented the evidence of a chemical bridge between the wood fiber and polymeric matrix through esterification. The feature peak of esterification occurred in the range between 1800 and 1650 cm(-1) at FTIR spectra. Succinic and half succinic esters were the two primary covalent bonding products to cross-link the wood fiber and thermoplastic matrix. Maleated composites had a remarkable shift on most O1s and C1s spectra in respect to the wood, HDPE, and untreated composites. The binding energy of maleated composites at C1s and O1s spectra was around 282 eV and 530 eV. respectively. The mass concentration of chemical components at the interface was related to the coupling agent type, structure, and concentration. According to the FTIR and ESCA analyses, the coupling mechanisms of MAPEs were proposed. The interfacial morphology in wood-fiber/HDPE composites was illustrated with the pinwheel models based on SEM observations.