Phosphonium chloride covalently bound to the fluorous polymer is proved to be an efficient and recyclable homogeneous CO₂-soluble catalyst for organic solvent-free synthesis of cyclic carbonates from epoxides and CO₂ under supercritical CO₂ conditions. The catalyst can be easily recovered by simple filtration after reaction and reused with retention of high activity and selectivity. In addition, the effects of various reaction variables on the catalytic performance are also discussed in detail. The process represents a simpler access to preparing cyclic carbonates with the ease of homogeneous catalyst recycling.