This study describes the experimental design and optimization of the photocatalytic reaction using the immobilized catalyst Fe/Nb2O5 in the degradation of Triclosan and 2.8-DCDD. The techniques employed to characterize the photocatalysts were: specific surface area, average pore volume, average pore diameter, photo-acoustic spectroscopy (PAS), X-ray diffraction (XRD), and scanning electron microscopy (SEM/EDS). The reaction parameters studied were pH, catalyst concentration, catalyst calcination temperature, and nominal metallic charge. The results indicated that the immobilized Fe/Nb2O5 catalysts were efficient in the degradation of Triclosan and 2.8-dichlorodibenzene-p-dioxin. The catalysts with nominal metal loading of 1.5% Fe calcined at 873 K showed the highest constant reaction rate and the lowest half-life 0.069 min−1 and 10.04 min. Tests in different matrices indicated that the photocatalytic reaction using aqueous solution containing Cl− is faster when compared with the ultrapure water matrix.