In summary, our development of a high-performance lithiated Si-S full cell system leverages the synergistic combination of a polymer-enhanced silicon (TzG@Si) anode and an organic polymer sulfur (S@PAN) cathode. Employing a compatible carbonate electrolyte, we established that both electrodes form a LiF-rich SEI layer, which crucially underpins the stability of the entire cell. The robustness of the polymer backbone in each electrode ensures structural integrity throughout cycling, effectively mitigating the challenges of volume expansion. Additionally, operando Raman spectroscopy confirmed the absence of sulfur dissolution and migration. The full cell delivered an energy density of 414.3 Wh kg -1 and demonstrated enduring cycle life, sustaining performance over 400 cycles. These results underscore the substantial promise of this full cell system for future industrial applications.