Antibiotics elimination by some photochemical processes involves ferric ions, but little is discussed about the fundamental aspects of complexation effects on their degradation. This study compares the photodegradation of two fluoroquinolones, three β-lactams, and their ferric complexes in deionized water. The complexed antibiotics were more recalcitrant than the free antibiotics to the solar light action (the photodegradation rate constants diminished by more than 50%). To better study the photodegradation, other experiments considering two representative cases (ciprofloxacin and dicloxacillin) were performed. For ciprofloxacin, as the iron amount was increased from 0 to 7.5 µmol L−1, its photodegradation rate constant decreased from 0.017 to 0.004 min−1. In contrast, for dicloxacillin, the increase in iron concentration (from 0 to 7.5 µmol L−1) accelerated its photodegradation (the rate constant augmented from 0 to 0.0026 min−1). When UVC light was used, the degradations of free and complexed antibiotics were very close, exhibiting values of degradation rate constants between 0.030 and 0.085 min−1. The antimicrobial activity (AA) was eliminated when 90% of ciprofloxacin and 90–95% of dicloxacillin were degraded. The AA removal was associated with structural changes in relevant moieties of antibiotics, such as fluorine and piperazyl ring for ciprofloxacin, or β-lactam ring for dicloxacillin.