The development of a free-standing electrode with high rate capability requires the realization of facile electrolyte percolation, fast charge transfer at the electrode-electrolyte interface as well as the intimate electrical wiring to the current collector. Employing a sulfonated high internal phase emulsion polymer (polyHIPE) as the carbon precursor, we developed a free-standing composite of carbon foam encapsulated SnO2 nanocrystallites, which simultaneously satisfies the aforementioned requirements. When directly evaluated in the pouch cell without using the binder, carbon additive or metallic current collector, the best performing composite exhibits a good rate performance up to 8 A g−1 and very stable cyclability for 250 cycles. This cycling performance was attributed to the synergistic coupling of hierarchical macro/mesoporous carbon foam and SnO2 nanocrystals with optimized size range. Postmortem characterizations unveiled the significant influence of subtle size variation of oxides on the electrochemical performance.