Mass transport process, adsorption and desorption, and electrochemical reaction were analyzed to investigate the mechanism of enhancement on boron-doped diamond (BDD) electrode electrochemical degradation efficiency by ultrasound (US). US has considerable influences on the above steps of electrochemical oxidation. Mass transport coefficients of Ph and PA reach 2.010-5 m/s with US, from 5.410-6 m/s and 6.710-6 m/s in EC process, increasing by 270% and 199%, respectively. The effect of US on adsorption and desorption has relationship with electrochemical adsorption properties of pollutants on BDD electrode surface. The adsorption amount of Ph decreases from 6.4910-10 mol/cm2 to 1.3910-10 mol/cm2, with the desorption of polymer intermediates promoted, so US makes positive effect with benefit to direct oxidation and oxidation peak current increases by 32%. For PA, the adsorption amount decreases from 1.2510-11 mol/cm2 to 3.1110-12 mol/cm2 with US, and no direct oxidation happens in US-EC process. US can improve degradation efficiency of BDD electrode and the enhancement on Ph degradation is more effective. Average electrochemical oxidation energy efficiency (AEE) of Ph increases by 287%, more than 224% of PA. This is because both direct and indirect oxidation for Ph can be enhanced by US, while for PA, direct oxidation almost disappears.