FePO4/graphene and LiFePO4/graphene hybrids have been synthesized by an eco-friendly RAAP-directed growth method. With this strategy, FePO4 and LiFePO4 particles have been grown on the exfoliated graphene-assembled scaffolds. Both of the hybrids present superior electrochemical properties, i.e., high rate capability combined with good capacity retention upon cycling, indicating the great potential as the cathode materials for Li-ion batteries.