In this study, TiO₂ was synthesized with different solvents and further immobilized on polyurethane (PU) foams. The effect of ethanol, isopropanol (IPA) and water (H₂O) on the synthesis of TiO₂ nano-photocatalysts by a rapid (10 min) microwave approach at 200 °C is reported. The structural, morphological, and optical properties of the TiO₂ nanopowders were further investigated. X-ray diffraction (XRD) revealed a mixture of phases (anatase/brookite and anatase/rutile) for the syntheses in IPA and H₂O and pure TiO₂ anatase phase in ethanol. SEM (Scanning Electron Microscopy) and STEM (Scanning Transmission Electron Microscopy) showed that the TiO₂ nanostructures synthesized in ethanol were composed of micrometer spherical aggregates with bulk defects, and surface defects on the high index surfaces, while the syntheses in IPA and H₂O resulted in one-dimensional (1D) structures and other nanocrystals with undefined shape. BET analysis confirmed that the specific surface area of the TiO₂ synthesized with ethanol was superior to the nanopowders synthesized with IPA and H₂O. XPS showed an enhanced capacity for surface oxygen adsorption for the nanopowders produced in alcohol-based solvents. In the presence of the TiO₂ nanopowder synthesized in ethanol, the contribution from the high surface area and density of defects, as well as high-index facets led to an enhancement in the removal of TC. PU foams were also functionalized with the TiO₂ nanopowder produced in ethanol through a simple dip-coating process. While dark phase adsorption studies showed negligible TC adsorption on the TiO₂-coated foam, light irradiation induced considerable TC degradation. Reusability tests revealed minimal efficiency loss over three consecutive cycles. Ecotoxicity assays using Artemia salina nauplii demonstrated low mortality rates (< 10%) with TiO₂-PU foams in 24 h, suggesting their safety. This study showcases the successful surface modification of PU foams with TiO₂ nanostructures, through low-cost and simple approaches with the aid of microwave irradiation, highlighting their potential for an efficient removal of antibiotics from aqueous systems, whereas maintaining ecological safety.