Fe2O3 is an appealing anode material due to its high specific capacity (1007 mAh g−1), low cost, natural abundance, and nontoxicity. However, its unstable structure during cycling processes has hindered its potential. In this study, we present a "green" synthesis method to fabricate stable porous Fe2O3 encapsulated in a buffering hollow structure (p-Fe2O3@h-TiO2) as an effective anode material for Li-ion batteries. The synthesis process only involves glucose as an "etching" agent, without the need for organic solvents or difficult-to-control environments. Characterizations of the nanostructures, chemical compositions, crystallizations, and thermal behaviors for the intermediate/final products confirm the formation of p-Fe2O3@h-TiO2. The synthesized Fe2O3 anode material effectively accommodates volume change, decreases pulverization, and alleviates agglomeration, leading to a high capacity that is over eleven times greater than that of the as-received commercial Fe2O3 after a long cycling process. This work provides an attractive, "green" and efficient method to convert commercially abundant resources like Fe2O3 into effective electrode materials for energy storage systems.