High-voltage initial anode-free lithium metal batteries (AFLMBs) promise the maximized energy densities of rechargeable lithium batteries. However, the reversibility of the high-voltage cathode and lithium metal anode is unsatisfactory in sustaining their long lifespan. In this research, a concentrated electrolyte comprising dual salts of LiTFSI and LiDFOB dissolved in mixing solvents of dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC) with a LiNO3 additive was formulated to address this challenge. FEC and LiNO3 regulate the anion-rich solvation structure and help form a LiF, Li3N-rich solid electrolyte interphase (SEI) with a high lithium plating/stripping Coulombic efficiency of 98.3%. LiDFOB preferentially decomposes to effectively suppress the side reaction at the high-voltage operation of the Li-rich Li1.2Mn0.54Ni0.13Co0.13O2 cathode. Moreover, the large irreversible capacity during the initial charge/discharge cycle of the cathode provides supplementary lithium sources for cycle life extension. Owing to these merits, the as-fabricated AFLMBs can operate stably for 80 cycles even at an ultrahigh voltage of 4.6 V. This study sheds new insights on the formulation of advanced electrolytes for highly reversible high-voltage cathodes and lithium metal anodes and could facilitate the practical application of AFLMBs.