Double compound modification was carried out for hypereutectic Al-24Si alloy. The experiment showed that double modification with phosphorus and rare earth can fine the structure of alloy. The complex modifications of phosphorus and rare earth make the coarse block primary silicon obviously refined and the large needle eutectic silicon modified to the fine fibrous or lamella ones. Phosphorus mainly refines the primary silicon. Rare earth can well refine the primary and eutectic silicon, but its modification effect on the eutectic silicon is more obvious. The alloys with the additions of 0.10% phosphorus and 0.9% rare earth have the optimal microstructure. Compared with the unmodified alloy, the primary silicon of alloys can be refined from 93.5 μm to 24.1 μm and the eutectic silicon can be refined from 8.5 μm to 5.3 μm. Mechanism of double compound modification with phosphorus and rare earth is discussed as well.