The oxygen evolution reaction (OER) is known as a kinetics barrier in electrochemical water splitting. Developing stabilized non-precious metal-based catalysts is crucial for the wide application of electrolytic water splitting in oxygen production. Porous Co-based intermetallics function as promising non-noble metal catalysts for OER. Porous nanogrid-like Cu-doped Co-based materials (D-CAC) were prepared via the combination of rapid self-exothermic reactions and subsequent chemical dealloying. The Co-Al intermetallics possess high porosity and large specific surface area, which can promote mass transfer. On the other hand, proper metal doping is beneficial to adjust the absorption and desorption of oxygen-containing intermediate species. Accordingly, the D-CAC sample exhibited excellent OER activity with an overpotential of 370 mV@10 mA cm-1 and a low Tafel slope of 52.7 mV dec-1 in 1 M KOH. These findings offer a novel perspective on the efficient development of cobalt-based electrocatalysts for oxygen evolution.