A graphene oxide (GO) membrane can be used in structural dielectric capacitors and planar micro-supercapacitors as a dielectric separator material due to its excellent through-plane and in-plane dielectric properties. The ability to tailor the dielectric properties of the GO membrane is crucial for dielectric applications. We believe this to be the first demonstration describing how Al3+ ions impact the dielectric properties of the GO membrane through cation to oxygenated functional groups interactions. In this study, the Al3+-modification to the GO membrane was realized through a facile pre-coordination method followed by layer-by-layer assembling. The influence of Al3+ on the GO membranes’ through-plane and in-plane dielectric properties (dielectric constant and dielectric loss) was investigated in the frequency range from 0.01 Hz to 105 Hz. Plane-to-plane and edge-to-edge Al3+coordination with the functional group on the basal plane or edge of the GO sheets was proposed to understand the metal ion's impact on the dielectric properties. The results demonstrated that the Al3+ modification was an effective strategy to tailoring the GO membranes’ dielectric properties in a low frequency regime and further suggested the possibility of designing dielectric GO membranes with controllable dielectric performance. At a low frequency range (0.01–1 Hz), the addition of Al3+ increased the through-plane dielectric constant and decreased the in-plane dielectric constant. In terms of dielectric loss, unmodified GO membranes exhibited a higher in-plane dielectric loss than the through-plane dielectric loss. Al3+-modified GO membranes exhibited increased through-plane dielectric loss and decreased in-plane dielectric loss compared to the unmodified GO membranes.