The rare earth molten salt electrolytic slag (REMSES) has recently attracted significant attention due to its potential environmental hazards and high content of rare earths and lithium, leading to a surge in recycling efforts. In this study, we propose and demonstrate a novel and straightforward process for the simultaneous extraction of rare earths and lithium from REMSES through lime transformation and sulfuric acid leaching at low temperatures. Firstly, during the lime transformation process, REMSES is converted into hydroxides that can be easily dissolved in acids. Secondly, REEs and Li present in the slag are co-extracted using a conditional sulfuric acid leaching method, resulting in 95.72% REEs leaching efficiency and 99.41% Li leaching efficiency under optimal conditions. Finally, REEs and Li in the solution are precipitated using oxalic acid and trisodium phosphate with precipitation efficiencies of 99.02% for REEs and 94.85% for Li respectively. This innovative process enables the conversion of REEs and lithium from REMSES into high-purity products (a mixture of REOs with 99.31% purity; Li₃PO₄ with 98.93% purity), thereby facilitating their valuable utilization.