So far, nanoscale superlubricity has been demonstrated in well-ordered van der Waals materials, such as graphite and mechanically exfoliated graphene. In contrast, this study demonstrates nanoscale superlubricity in structurally inhomogeneous systems such as solution-processed graphene films, which are promising for scalable and practical applications. The investigated graphene films were obtained via liquid-phase exfoliation (LPE) and deposited by Langmuir–Blodgett assembly technique at the water–air interface, while frictional measurements were performed using atomic force microscopy (AFM)-based techniques. To enable superlubricity in the system consisting of a silica AFM tip and an LPE graphene film, a tribo-induced, graphene-based conformal coating was first formed around the tip. Unlike previous studies that relied exclusively on pristine graphite, we easily transferred small and weakly adhered graphene flakes onto the AFM tip by rubbing it against the LPE graphene film in contact mode. Subsequent friction measurements were performed using these graphene-coated tips. The measurements on LPE films deposited onto silica and polyethylene terephthalate (PET) substrates revealed ultralow friction coefficients of approximately 0.005 on flat regions composed of large graphene flakes thereby confirming the emergence of the superlubric regime. However, the inherently non-uniform morphology of LPE films, with small flakes and numerous exposed edges, introduces localized high-friction regions and wear-prone sites that prevent superlubricity across extended areas. These findings highlight the importance of achieving large flake sizes with reduced density of exposed edges and improved flake adhesion in order to enable robust structural superlubricity in LPE graphene films.