Herein, the electronic structure of RhCu nanospheres was optimized and the size of the nanoparticles was reduced by an ultrasonic-assisted hydrothermal method. The performance of electrocatalytic urea synthesis was improved with an enhanced faradaic efficiency and urea yield rate of 34.82 ± 2.47% and 26.81 ± 0.62 mmol g-1 h-1, respectively. This work opens a novel insight into synthesizing an electrocatalyst by ultrasonic treatment for urea production.