Amorphous　transition　metal　oxides　have　recently　received　particular　research　interests　in　electrochemical　energy　storage.　However,　there　is　still　a　lack　of　direct　comparisons　between　amorphous　materials　and　their　crystalline　counterparts.　Here,　we　demonstrate　the　rational　synthesis　of　crystalline　and　amorphous　Fe2O3　nanocubes　uniformly　grown　on　carbon　nanofibers　(denoted　as　CNFs@C-Fe2O3　and　CNFs@A-Fe2O3,　respectively)　for　lithiumion　batteries　(LIBs)　and　lithium-sulfur　batteries　(LSBs).　In　such　a　structure,　the　Fe2O3　nanocubes　possess　strong　interfacial　bonding　with　CNFs,　which　can　ensure　rapid　electron　transportation.　Besides,　these　Fe2O3　nanocubes　are　highly　porous,　which　can　effectively　alleviate　the　volume　change,　enlarge　the　surface　area,　increase　active　sites　and　facilitate　ion　diffusion.　When　employed　as　freestanding　anode　for　LIBs,　the　CNFs@C-Fe2O3　electrode　delivers　much　improved　lithium　ion　storage　performance　compared　to　that　of　CNFs@A-Fe2O3.　When　evaluated　as　interlayers　for　LSBs,　instead,　the　batteries　with　CNFs@A-Fe2O3　exhibit　better　rate　performance　cycling　stability　than　that　of　with　CNFs@C-Fe2O3.　Moreover,　theoretical　calculations　elucidate　the　amorphous　Fe2O3　has　stronger　adsorption　ability　toward　the　soluble　lithium　polysulfides.　This　work　would　provide　new　insights　into　the　reasonably　development　of　crystalline　and　amorphous　transition　metal　oxides　toward　electrochemical　energy　storage.