The instability of P─F bond-based electrolyte (PFE) under ambient conditions presents one of the biggest challenges for the production, usage, and recycling of lithium (Li) batteries. It increases the cost of battery production, decreases battery service life, and harms human health and environmental sustainability during the use of batteries. Here a stabilized P─F bond electrolyte (SPFE) is reported, which can effectively prevent the side-reactions in PFE at ambient conditions. The SPFE, which is pristine, containing ultra-high content of water (10 000 ppm or 10 g L−1), can support the 2 Ah Li-ion pouch cell (200 Wh kg−1) cycling 400 times with 90.2% of its capacity retained. The mostly dry room-free (DRF) production of commercial Li-ion (2Ah, 200 Wh kg−1) and anode-free (AF) Li metal pouch cell (2 Ah, 410 Wh kg−1) also demonstrated excellent cycling stability with the SPFE. Moreover, the SPFE enables AF Li-metal batteries (AFLMBs) to retain 54.1% of their charged capacity even after 180 days of open circuit storage. By intrinsically safeguarding PFE from hydrolysis, the present SPFE would have a broad impact on future battery technology, simplifying battery production, extending battery service life, and safeguarding battery recyclability.