Ensuring interfacial stability of Si-containing anodes and Ni-rich cathodes is the key to achieving highenergy lithium-ion cells. Herein, we present 4-(allyloxy)phenyl uorosulfate (APFS), a multi-functional electrolyte additive that forms a mechanical strain-adaptive solid electrolyte interphase (SEI) composed of LiF and polymeric species, and a thermally stable cathode-electrolyte interface containing S-O and S-F species. Radical copolymerization of vinylene carbonate (VC) with APFS via electrochemical initiation creates a spatially deformable polymeric SEI on the Si/C-graphite (SiG-C) anode with large volume changes during cycling. Here we show that APFS-promoted interfacial layers reduce Ni dissolution and deposition and that APFS deactivates Lewis acidic PF 5 , inhibiting the hydrolysis that produces unwanted HF. These results show that the combined use of VC and APFS allows capacity retention of 72.5% with a high capacity of 143.5 mAh g − 1 after 300 cycles at 45°C.