Oxygen evolution reaction (OER) is one of the most important reactions in the energy storage devices such as metal–air batteries and unitized regenerative fuel cells (URFCs). However, the kinetically sluggishness of OER and the high prices as well as the scarcity of the most active precious metal electrocatalysts are the major bottleneck in these devices. Developing low-cost non-precious metal catalysts with high activity and stability for OER is highly desirable. A facile, in situ template method combining the dodecyl benzene sulfuric acid sodium (SDBS) assisted hydrothermal process with subsequent high-temperature treatment was developed to prepare porous Co3O4 with improved surface area and hierarchical porous structure as precious catalysts alternative for oxygen evolution reaction (OER). Due to the unique structure, the as-prepared catalyst shows higher electrocatalytic activity than Co3O4 prepared by traditional thermal-decomposition method (noted as Co3O4-T) and commercial IrO2 catalyst for OER in 0.1 M KOH aqueous solution. Moreover, it displays improved stability than Co3O4-T. The results demonstrate a highly efficient, scalable, and low cost method for developing highly active and stable OER electrocatalysts in alkaline solutions.