The low electrocatalytic activity of pristine graphite felt (GF) electrodes toward V(II)/V(III) and V(IV)/V(V) redox couples is a major concern in vanadium redox flow batteries (VRFBs). For overcoming this challenge, herein a novel composite electrode is proposed comprising of two components: multidimensional frame carbon (MFC) derived from edge‐rich carbon and GF that serves as the frame for the in situ growth of MFC. The high electrocatalytic activity, rapid charge migration, and reduced local current emanating from the 0D, 2D, and 3D coexistent structures of the MFC material, respectively, enhance the performance of the GF. Consequently, the battery assembled using the MFC GF electrode achieves a maximum current density of 500 mA cm−2, along with high stability and preeminent energy efficiency at a current density of 200 mA cm−2 for over 400 cycles. For the first time via density functional theory analysis on VRFBs, this study reveals that the edge‐rich carbon atoms possess higher electrocatalytic activity in both positive and negative electrolytes than the plane carbon atoms and heteroatoms. Therefore, this study is of immense significance in guiding and promoting the application of edge‐rich carbon in the battery‐based energy storage industry.

High-energy-density lithium metal batteries with high safety and stability are urgently needed. Designing the novel nonflammable electrolytes possessing superior interface compatibility and stability is critical to achieve the stable cycling of battery. Herein, the functional additive dimethyl allyl-phosphate and fluoroethylene carbonate were introduced to triethyl phosphate electrolytes to stabilize the deposition of metallic lithium and accommodate the electrode–electrolyte interface. In comparison with traditional carbonate electrolyte, the designed electrolyte shows high thermostability and inflaming retarding characteristics. Meanwhile, the Li||Li symmetrical batteries with designed phosphonic-based electrolytes exhibit a superior cycling stability of 700 h at the condition of 0.2 mA cm−2, 0.2 mAh cm−2. Additionally, the smooth- and dense-deposited morphology was observed on an cycled Li anode surface, demonstrating that the designed electrolytes show better interface compatibility with metallic lithium anodes. The Li||LiNi0.8Co0.1Mn0.1O2 and Li||LiNi0.6Co0.2Mn0.2O2 batteries paired with phosphonic-based electrolytes show better cycling stability after 200 and 450 cycles at the rate of 0.2 C, respectively. Our work provides a new way to ameliorate nonflammable electrolytes in advanced energy storage systems.