The invention discloses a prussian blue analog anode catalyst with hollow cubic structure and prepn. method thereof, the prepn. method has the advantages of uniform heating, easy control, low raw material cost, easy access to target products, good morphol. of the hollow structure PBA obtained, excellent OER performance of electrolyzing water and UOR performance of electrolyzing urea. The invention synthesizes PBA with cubic structure by pptn. method, etching PBA cube by anhyd. ethanol by hydrothermal method to obtain hollow PBA with cubic structure.