Superlattices have attracted great interest because of their tailorable electronic properties at the interface. However, the lack of an efficient and low-cost synthetic method represents a huge challenge to implement superlattices into practical applications. Herein, we report a space-confined nanoreactor strategy to synthesize flexible freestanding graphene-based superlattice nanosheets, which consist of alternately intercalated monolayered metal-oxide frameworks and graphene. Taking vanadium oxide as an example, clear-cut evidences in extended X-ray absorption fine structure, high-resolution transmission electron microscopy and infrared spectra have confirmed that the vanadium oxide frameworks in the superlattice nanosheets show high symmetry derived from the space-confinement and electron-donor effect of graphene layers, which enable the superlattice nanosheets to show emerging magnetocaloric effect. Undoubtedly, this freestanding and flexible superlattice synthesized from a low-cost and scalable method avoids complex transferring processes from growth substrates for final applications and thus should be beneficial to a wide variety of functionalized devices.