Tuning material properties by modulation of the arrangement of atoms is a fundamental and effective strategy in materials science. Structurally long-range ordered materials are increasingly finding utility for electrocatalytic applications. Such ordered structures can achieve unique functions that increase the electrocatalytic activity compared to corresponding electrocatalysts with a disordered structure. Effective strategies for designing high-performance electrocatalysts based on structurally ordered materials are presented. This review also summarizes the recent progress on structurally ordered materials as efficient electrocatalysts and highlights the applications in several representative electrochemical reactions, such as, the oxygen evolution reaction, oxygen reduction reaction, and hydrogen evolution reaction. The structural features of the atomic long-range ordered framework and superior electrochemical performance are demonstrated by advanced characterization techniques (structural identification) and electrochemical measurements (performance evaluations), respectively. Special attention is paid to the establishment of a structure-activity relationship to highlight the advantages of the ordered structure. Finally, the remaining challenges and emerging opportunities in these related materials are proposed.