The development of disordered Li dendrite and the adverse reaction between Li and electrolyte impede practical use of Li metal batteries (LMB). Herein, we propose quasi-two-dimensional fluorinated metal-organic framework carbon (q2D-FcMOF) that is utilized to construct artificial solid electrolyte interface (ASEI) to achieve robust interfacial protective double-layer. The outer organic layer provides ample space for Li deposition, while the inner inorganic LiF layer promotes conduction of Li+ and blocks electron transport. Metal clusters within the hybrid layer are uniformly dispersed, encouraging Li+ to cluster around metal active sites that are thermodynamically compatible with Li. Consequently, q2D-FcZ8@Li symmetrical batteries demonstrate an ultralong cycle life over 3600 h. When paried with commercial cathodes, the cells exhibite cyclability under conditions of high-loading, lean-electrolyte, even exposure to air for some time. This research suggests an effective method for fabricating ASEI using 2D quasi-ordered superstructure MOF NPs, which is expected to the development of LMB. The Li dendrites and adverse Li-electrolyte reactions hinder the practical use of Li metal batteries. Here, authors propose an organic/inorganic artificial solid electrolyte interphase, where an outer metal layer ensures uniform Li nucleation and a F-rich inner layer acts as an electronic insulator.