Abstract Surface modification is frequently used to solve the problems of low combustion properties and agglomeration for aluminum‐based fuels. However, due to the intrinsic incompatibility between the aluminum powder and the organic modifiers, the surface coating is usually uneven and disordered, which significantly deteriorates the uniformity and performances of the Al‐based fuels. Herein, a new approach of monolayer nano‐vesicular self‐assembly is proposed to prepare high‐performance Al fuels. Triblock copolymer G‐F‐G is produced by glycidyl azide polymer (GAP) and 2,2′‐(2,2,3,3,4,5,5‐Octafluorohexane‐1,6‐diyl) bis (oxirane) (fluoride) ring‐open addition reaction. By utilizing G‐F‐G vesicular self‐assembly in a special solvent, the nano‐sized vesicles are firmly adhered to the surface of Al powder through the long‐range attraction between the fluorine segments and Al. Meanwhile, the electrostatic repulsion between vesicles ensures an extremely thin coating thickness (≈15 nm), maintaining the monolayer coating structure. Nice ignition, combustion, anti‐agglomeration, and water‐proof properties of Al@G‐F‐G(DMF) are achieved, which are superior among the existing Al‐based fuels. The derived Al‐based fuel has excellent comprehensive properties, which can not only inspire the development of new‐generation energetic materials but also provide facile but exquisite strategies for exquisite surface nanostructure construction via ordered self‐assembly for many other applications.