The durable red phosphorus (RP) anode for lithium-ion batteries (LIBs) has attracted great attention owing to its high theoretical specific capacity (2596 mA∙h∙g⁻¹) and moderate lithiation potential (~ 0.7 V vs. Li⁺/Li). However, its intrinsic poor electrical conductivity, enormous volume expansion, and soluble intermediates (lithium polyphosphides, Li_xPP_s) lead to poor cycling performance. To overcome these issues, we introduce a new type of wrinkle carbon spheres as the host for loading phosphorus through a vaporization–condensation strategy. Density functional theory calculations reveal that the wrinkle carbon sphere shows strong binding energy with P₄ molecule, accelerating the adsorption and polymerization of P₄, thus enhancing RP conversion in the preparation process. In the lithiation/delithiation process, the wrinkle carbon has strong bonding with phosphorus and strong adsorption with Li_xPP_s, resulting in excellent cycling performance. The design strategy to modify RP polymerization via reforming the interaction between wrinkle carbon spheres and phosphorus expands the application of RP for LIBs and beyond.