The increasing amounts of pharmaceuticals in aqueous environment are found to be structurally diverse. 03 has been demonstrated as a high effective agent in removing pharmaceuticals, however, 03 is a very selective oxidant which is ineffective for some ozone refractory structures. Recently, a novel electrochemistry-based oxidation process (E-peroxone) has been- developed by a simple combination of electrolysis and conventional ozonation process, which can produce a large amount of aqueous (OH)-O-center dot in situ. E-peroxone process can enhance the performance of conventional ozonation process. The purpose of this study was to investigate the elimination performance of thirty pharmaceuticals with various chemical structures including macrolide, quinolone, sulfonamides, tetracycline, carboxylic group, Naphthalene, Nitrogen-containing group, C=C double bond in electrolysis, ozonation and E-peroxone process. Parent pharmaceuticals and TOC elimination were compared. By comparing different chemical groups, the synergy effect of pharmaceuticals with carboxylic and amide groups were significant, with average degradation level 98.7 2.8% within 15 min. Degradation levels of some groups were quite efficient during both ozonation and E-peroxone process, such as macrolide, quinolone, sulfonamides and tetracycline. E-peroxone process improved the TOC and acute toxicity elimination efficiency of mixed pharmaceutical solutions significantly. Major operation parameters and cross correlation analysis were also evaluated.