Layered　double　hydroxide　(LDH)　materials　have　emerged　as　perspective　anode　catalysts　for　the　electrocatalytic　oxygen　evolution　reaction　(OER)　to　substitute　the　high-price　noble　metal　catalysts.　However,　the　OER　performance　of　LDH　is　unsatisfactory　as　a　result　of　its　limited　electroconductivity　and　sluggish　surficial　water　oxidation　kinetics.　Here,　we　reported　a　Fe2O3/CoFe-LDH　heterostructure　electrocatalyst　through　a　facile　hydrothermal　process.　By　in　situ　decorating　CoFe-LDH　with　Fe2O3nanospheres,　a　boosted　electrocatalytic　OER　performance　is　evidenced　from　the　Fe2O3/CoFe-LDH　catalysts　with　an　overpotential　of　240　mV　for　the　benchmarked　current　density　and　a　Tafel　slope　of　70.3　mV　dec-1.　As　a　result　of　the　uniquely　matched　energy　band　alignments　between　Fe2O3and　CoFe-LDH,　a　Fe2O3/CoFe-LDH　interfacial　type-II　heterojunction　is　evidenced.　As　such,　the　heterojunction-induced　charge　transfer　driving　force　greatly　enhances　the　charge　transfer　capability　of　Fe2O3/CoFe-LDH,　thus　improving　the　OER　performance.　This　work　offers　a　novel　approach　toward　enhancing　the　electron　transfer　kinetics　of　general　semiconductor-based　catalysts　by　rational　heterojunction　engineering.　©　2022　American　Chemical　Society.　All　rights　reserved.