Practical application of a Si anode in a high-energy-density battery cannot be achieved due to the huge volume expansion of these anodes. Researchers have focused on adding binders to the anode to restrict volume expansion in order to address this issue, as the hydrogen bonds and mechanical properties of binders can be used to enhance adhesion and accommodate the volume changes of a Si anode. Herein, we comprehensively consider binders' hydrogen bonds, mechanical properties, stability, and compatibility with the electrolyte solution, and design an ether-/ester-/fluorine-rich composite polymer, P(TFEMA-co-IBVE). The proposed binder formula possesses outstanding stability, adhesion, and mechanical strength; moreover, it can accommodate the dramatic volume changes of a Si electrode and exhibits excellent electrochemical performance, achieving a high areal capacity of about 5.4 mA∙h∙cm⁻². This novel polymer design may be applied to other electrode materials in the next generation of lithium-ion batteries.