In this work, we have successfully synthesized an efficient and cost-effective electrocatalyst for alkaline oxygen evolution (OER) using a solvothermal method combined with an ion exchange strategy. Firstly, single Co-layer hydroxides (Co-LHs) were synthesized by a one-step solvothermal method. Subsequently, [Fe(C2O4)3]3- was introduced onto the Co-LHs surface to facilitate ion exchange, and a further CoFe-layered double hydroxides (CoFe-LDHs) layer was grown on the Co-LHs material surface to finally obtain the nanoflower-like Co-LHs@CoFe-LDHs composite. Related material characterization results showed that C2O42- was successfully inserted into the interlayer structure of the LDHs, resulting in an increase in interlayer spacing. In situ Raman spectroscopy revealed that the active site of the OER reaction in the Co-LHs@CoFe-LDHs material was CoOx. Thanks to the double structure of the LDHs improving charge transfer ability and the synergy between cobalt and iron species, Co-LHs@CoFe-LDHs showed significantly enhanced OER performance. This study provides new insights and methods for the development of novel LDHs structural electrocatalysts.