In this study structured photocatalytic systems were successfully developed by a facile method. Polymeric (Alginate) molds, settled the basis in order to effectively disperse and stabilize nanoparticles of an efficient, copper augmented photocatalyst (Degussa P25), which after removal of the polymer by a pyrolytic or calcination-sintering procedure, were shaped in the form of all-ceramic hollow fibers (HFs) with enhanced photocatalytic and mechanical properties and excellent resistance to attrition. The structural and morphological properties have been studied using LN2 porosimetry, XRD, SEM and Raman spectroscopy. The experimental campaign for elucidating the photocatalytic performance encompassed batch experiments, where the abatement of a prototype organic pollutant (Methyl Orange) was investigated in the dark and under UV irradiation. The obtained performance was benchmarked against that of a prototype photocatalyst implemented in slurry or thin film reactors. The role and the contribution of zero-valent Cu nanoparticles in the photocatalytic mechanism, as well as of carbon residues from the pyrolytic procedure, were also examined.