Abstract: The interlayer bonding of graphene oxide (GO) is a key factor determining the macroscopic tribological properties of its solid lubricating coatings. In this study, a series of GO self-assembled coatings were controllably prepared under the coordination of different metal ions (Li⁺, Ca²⁺, Al³⁺), and the friction and wear properties of the GO coatings were evaluated in atmospheric, nitrogen, and vacuum environments. Meanwhile, the regulation mechanism of the interlayer bonding of the GO coatings was explored. It was found that the cross-linking effect between metal ions and GO could improve the tribological properties of the coatings, and the valence state of metal cations would directly affect the mode and magnitude of the cross-linking effect. The experimental results showed that introducing metal ions could significantly increased the bonding force between the lamellae, reduce the deterioration of oxygen-containing functional groups on GO, passivate surface defects, and improve tribological properties. The higher the valence state was, the more significant the improvement in the tribological properties of the metal ion self-assembled GO coatings would be. The trivalent GO-Al³⁺ coatings exhibited more excellent tribological properties in atmospheric, nitrogen, and vacuum environments.