Anode-free Li-metal batteries (AFLBs) are of significant interest to energy storage industries due to their intrinsically high energy. However, the accumulative Li dendrites and dead Li continuously consume active Li during cycling. That results in a short lifetime and low Coulombic efficiency (CE) of AFLBs. Introducing effective electrolyte additives can improve the Li deposition homogeneity and solid-state interphase (SEI) stability for AFLBs. Herein, we reveal that introducing dual additives, composed of LiAsF6 and FEC, into a commercial carbonate electrolyte will boost the cycle life and average CE of NCM||Cu AFLBs. The NCM||Cu AFLBs with the dual additives exhibit a capacity retention of about 75% after 50 cycles, much higher than those with bare electrolytes (35%). The average CE of the NCM||Cu AFLBs with additives can maintain 98.3% over 100 cycles. In contrast, the average CE without additives rapidly decline to 97% after only 50 cycles. In situ Raman measurements reveal that the prepared dual additives facilitate denser and smoother Li morphology during Li deposition. The dual additives significantly suppress the Li dendrite growth, enabling stable SEI formation on anode and cathode surfaces. Our results provide a broad view of developing low-cost and high-effective functional electrolytes for high-energy and long-life AFLBs.