Although over the past few years, graphene oxide (GO) has emerged as a promising membrane material, the applicability of layered GO membranes in water purification/seawater desalination is still a challenging issue because of the undesirable swelling of GO laminates in the aqueous environment. One of the ways to tune the interlayer spacing and to arrest the undesirable swelling of layered GO membranes in the aqueous environment is to intercalate the interlayer spacing of the GO laminates with cations. Although the cation intercalation imparts stabilization to GO laminates in the aqueous environment, their effect on the performance of the membrane is yet to be addressed in detail. In the present study we have investigated the effect of cation intercalation on the performance of layered GO membranes using molecular dynamics simulation. For the same interlayer spacing, the cation intercalated layered GO membranes have a higher water flux as compared to the corresponding pristine layered GO membranes. In the presence of the cations, the water molecules inside the interlayer gallery get more compactly packed. The presence of the cations also increases the stability of the hydrogen bond network among the water molecules inside the membrane. This can be attributed to slow water reorientation dynamics inside the interlayer gallery in the presence of the cations. The synergistic effect of all these changes is that the water permeability through the cation intercalated layered GO membranes is higher as compared to that through the corresponding pristine layered GO membranes. On the other hand, the intercalation of the cations (K⁺, Mg²⁺) leads to higher rejection of Na⁺ ions whereas the rejection of Cl⁻ ions slightly decreases.