In this study, pure TiO2 gels were synthesized by applying the sol–gel method, using Ti(IV) butoxide with the addition of two different solvents, namely ethylene glycol (EG) and isopropanol (isop), with only air moisture present. It was established using XRD that the gel prepared with the addition of EG was amorphous even at 400 °C, while the other gel was amorphous up to 300 °C. It was found that TiO2 (anatase) had a dominant crystalline phase during heating to 600 °C, while at 700 °C, TiO2 (rutile) appeared. The as-obtained powdered materials were annealed at 500 °C and subsequently underwent photocatalytic tests with paracetamol. Additionally, the TiO2 samples were modified with Ag+ co-catalysts (10−2 M), using photofixation by UV illumination. The photocatalytic activity of the Ag-modified powders was also tested in the photodegradation of a commonly used paracetamol in aqueous solution under UV light illumination. The obtained data exhibited that the annealed samples had better photocatalytic efficiency and decomposed paracetamol faster in comparison to the non-annealed sol–gel powders. The highest degradation efficiency was observed for the TBT/isop/Ag material, with degradation efficiencies average values of 65.59% and 75.61% paracetamol achieved after the third cycle of photocatalytic treatment. The co-catalytically modified powders had higher photocatalytic efficiency in comparison to the pure nanosized powders. Moreover, the sol–gel powders of TBT/EG, TBT/EG/Ag (10−2 M), TBT/isop, and TBT/isop/Ag (10−2 M) demonstrated the ability to retain their photocatalytic activity even after three cycles of use, suggesting that they could find practical use in the treatment of pharmaceutical wastewater. The observed photocatalytic efficiency and positive impact of silver make the prepared powders a desirable choice for pharmaceutical drug degradation, helping to promote environmentally friendly and effective wastewater treatment technology.