For many advanced energy technologies, it is essential to produce non-precious metals, high activity, and low charge transfer resistance electrocatalysts through low cost and simple methods. In this work, MoSe₂-CoSe₂@CoAl-LDH composite was synthesized by a one-step hydrothermal method. Compare with the CoAl-LDH catalyst, the prepared MoSe₂-CoSe₂@CoAl-LDH composite exhibits an excellent OER performance with a low overpotential (320 mV at 10 mA·cm⁻²), a small Tafel slope (71 mV·dec⁻¹). The prominent OER performance of the MoSe₂-CoSe₂@CoAl-LDH composite can be mainly attributed to the fast electron transfer from the CoAl-LDH to MoSe₂-CoSe₂ and the catalytic activity promoted by the energy change of Co²⁺ due to the introduction of Se, which can be confirmed by EIS and XPS results, respectively. The strategy of this work may provide a low-cost and facile way for large-scale synthesis of non-precious metal modified hydrotalcite composite.