This study focuses on polymer−metal joints consisting of isotactic polypropylene (iPP) or iPP grafted with maleic anhydride (iPP-g-MA) and hydroxylated γ-Al 2 O 3 , which is a model for an oxidized aluminum surface, and investigates the contributions of the Young's moduli of iPP and iPP-g-MA and chemical functionality (MA groups) in iPP-g-MA to the interfacial failure behaviors using the molecular dynamics (MD) simulation method. First, our calculations demonstrated that the tensile strength observed in interfacial failures of the joints increases as Young's modulus of the polymer in the joints increases. This is because a higher stiffness makes it harder for a void to form within the polymer matrix under the applied tensile strain and to reach the interface. Second, in iPP-g-MA−γ-Al 2 O 3 joints, MA groups work more effectively to improve the interfacial strength as the Young's modulus of the polymer in the joints increases. For iPP-g-MA with a lower Young's modulus, the polymer molecules are pulled off the surface in a peel mode with increasing normal strain due to their greater flexibility. This results in a gradual removal of the MA groups and thus reduces their contribution. Meanwhile, for a higher Young's modulus, iPP-g-MA molecules at the interface are removed in a tensile mode because of their increased stiffness. This leads to more MA groups required to be detached from the surface at the same time to cause interfacial failure, thus increasing the contributions of the MA groups.