Fabricating electrode materials with superior electrochemical performance remains a challenge. Here, a simple but effective strategy for the formation of metal oxide nanomaterials with superior performance has been developed. Silk protein nanofibers adhered on reduced graphene oxide (rGO) sheets are used as templates to regulate the formation of nanostructured iron oxide composites, achieving porous nanorod structures that could not be attained in control experiments. These porous nanorods demonstrate superior electrochemical performance as electrodes with retention of a capacity of 1495 mAh g(-1) after 180 cycles at 0.2 C and a rate capability of 900 mAh g(-1) at 2 C discharge rate. These new rGO/silk composite templates provide a more controllable environment for Fe2O3 fabrication, resulting in improved nanostructures and superior electrical performance. The strategy developed here should also be more broadly applicable in the design of metal oxide nanomaterials with specialized structures and useful performance.