An ever-increasing energy demand has stimulated intense research into electrochemical technologies for both energy storage and conversion such as unitized regenerative fuel cells (URFCs). Due to its high efficiency, low cost, and low environmental impact, the URFC, which combines a polymer electrolyte membrane fuel cell (PEMFC) with a polymer electrolyte water electrolyzer (PEWE), has been regarded as an important energy technology that can offer new opportunities to not only further reduce investment costs but also to open doors to the mass production of domestic applications. Despite this, URFCs still have to be further improved and optimized to reach a level of maturity of both fuel cells and electrolyzers in terms of energy efficiency and long-term performance. Currently, the major challenge of URFC technology has been the insufficient performance of the bifunctional electrocatalyst. Based on the most recent research trends and progresses of bifunctional oxygen catalyst materials, this review will provide a systematic introduction and a comprehensive assessment of various bifunctional oxygen catalysts; their science and technology, including material selection, synthesis, and characterization, as well as their applications in URFCs. This review aims to correlate the physicochemical characteristics of URFCs with the catalytic activity/stability of these materials.