Harnessing their excellent physical attributes, two-dimensional nanostructures have gained prominences as reinforcements in polymer nanocomposites. Given the intricate structure of nanofillers and the varied interfacial connections, in-depth understanding of the strengthening mechanisms becomes pivotal for optimizing nanocomposite design. By varying the GO's morphology, a notable divergence of approximately 30% is evident in the interfacial shear strength. This divergence is attributed to the mechanical interlocking effect instigated by the presence of -O- and -OH functional groups. Functionalizing with groups like -CH3-CH2-NH2 (-Ethylamine) and -(HOCH2)3CNH2 (-TRIS) enhances the mass density of PE polymers at the interphase, which changes the interface sliding (low-density interphase) to the cohesive sliding during the pull-out process. As a result, the maximum interfacial shear strength (204â223 MPa) of these two samples is much larger than that of the pristine GO/PE (149â151 MPa), and even comparable with the pure PE's tensile strength. Intriguingly, shorter or highly flexible functional group exhibit a comparatively weaker influence on the interfacial shear strength. Moreover, as the sliding surface shifts toward the cohesive zone, diminishing sample thickness (less than 60 Ă ) generally corresponds to augmented interfacial shear strength due to the boundary confinement effect. In summary, this work offers a comprehensively elucidation of GO/PE pull-out behavior, facilitating the design of nanocomposites with exceptional mechanical performance.