This study investigates the degradation of the β-blockers in hospital wastewater by direct ozonation and Fe²⁺/ozonation with a focus on measurements at different initial pHs and Fe²⁺ concentrations, and the determination of kinetic constants. The results showed that these 'emerging contaminants' were completely degraded, when the removal rate of organic matter reached 30.6% and 49.1% for ozonation and Fe²⁺/ozonation, respectively. Likewise, the aromaticity removal rates were 63.4% and 77.9% for ozonation and Fe²⁺/ozonation, respectively. The experimental design showed that pH was the variable which had the greatest effect on the Fe²⁺/ozonation. The kinetic constants of atenolol, metoprolol and propranolol degradation by direct ozonation complied with pseudo-first-order conditions, while Fe²⁺/ozonation was suited to a biphasic degradation model. The k_obs tended to rise when the pH increases; propranolol showed high k_obs, which can be attributed to the naphthalene group (an electron-rich moiety). The identification of degradation products was carried out in aqueous solution using HPLC-MS², followed by a suggestion of degradation pathways by means of ozonation. The degradation products proved to be dependent on the initial pH, and followed pathways that are based on direct ozonolysis and free radicals.