Graphene, an important two-dimensional nanomaterial, is drawing unprecedented, worldwide attention, especially in electronics, energy storage, environmental science and biological engineering. We herein report a convenient protocol for forming a high-quality graphene/graphene oxide (GO) thin membrane on solid-state substrate via the Langmuir-Blodgett self-assembly technique. The process includes layer formation at the liquid-solid-air interface, pulling solid-state substrate vertically from the interface and chemical reduction of the membrane (selective process). Parameters which may alter the properties of membrane have been investigated. The pH was considered the most crucial factor since it affected the smoothness and continuity of the membrane. Pulling cycles had pronounced influence on the thickness of the membrane. Direct formation of the graphene-based membrane on solid-state substrates may eliminate concerns about metal particle residue from the graphene transfer process, incomplete removal of the organic chemicals, and assure the intactness and continuity of the graphene/GO layer. It is therefore believed that the procedure may shed light on the fabrication of high-quality graphene nanodevices.