The degradation efficiencies and pathways of metronidazole (MNZ) and amoxicillin (AMX) in binary mixtures by UV/TiO2 photocatalysis were studied. The presence of AMX significantly decreased the degradation of MNZ, whereas the existence of MNZ slightly reduced the degradation of AMX. This is basically due to the difference in attack ability of oxidizing agents present during TiO2 photocatalysis. All oxidizing agents (hydroxyl radicals, superoxide radicals, and holes) could attack AMX molecules, but hydroxyl radicals showed insignificant attack ability in MNZ degradation. In TiO2 photocatalysis of binary mixture, six transformation products were recognized by a high-resolution LC-QTof/MS. Because of competitive effect, only one product was sourced from MNZ degradation and four others were formed due to AMX degradation. The remaining one was a new product of the side reaction. This work indicated that the molecular structure of AMX determined its preferred degradation in a mixture. It not only affected the removal of antibiotics but also figured out the appearance of transformation products. In contrast to single systems, the extent of degradation reduced for each antibiotic in the presence of the second antibiotic was related to the availability of degradation pathways of each antibiotic. Moreover, suitable pH programming was applied to enhance the mineralization of the mixtures.