Abstract Fe 3 O 4 nanocrystals confined in mesocellular carbon foam (MSU‐F‐C) are synthesized by a “ host–guest ” approach and tested as an anode material for lithium‐ion batteries (LIBs). Briefly, an iron oxide precursor, Fe(NO 3 ) 3 ·9H 2 O, is impregnated in MSU‐F‐C having uniform cellular pores ∼30 nm in diameter, followed by heat‐treatment at 400 °C for 4 h under Ar. Magnetite Fe 3 O 4 nanocrystals with sizes between 13–27 nm are then successfully fabricated inside the pores of the MSU‐F‐C, as confirmed by transmission electron microscopy (TEM), dark‐field scanning transmission electron microscopy (STEM), energy dispersive X‐ray spectroscopy (EDS), X‐ray diffraction (XRD), and nitrogen sorption isotherms. The presence of the carbon most likely allows for reduction of some of the Fe 3+ ions to Fe 2+ ions via a carbothermoreduction process. A Fe 3 O 4 /MSU‐F‐C nanocomposite with 45 wt% Fe 3 O 4 exhibited a first charge capacity of 1007 mA h g −1 (Li + extraction) at 0.1 A g −1 (∼0.1 C rate) with 111% capacity retention at the 150 th cycle, and retained 37% capacity at 7 A g −1 (∼7 C rate). Because the three dimensionally interconnected open pores are larger than the average nanosized Fe 3 O 4 particles, the large volume expansion of Fe 3 O 4 upon Li‐insertion is easily accommodated inside the pores, resulting in excellent electrochemical performance as a LIB anode. Furthermore, when an ultrathin Al 2 O 3 layer (<4 Å) was deposited on the composite anode using atomic layer deposition (ALD), the durability, rate capability and undesirable side reactions are significantly improved.