In here we depict the morphogenesis and associated properties of TiO2-based macroscopic fibers designed for the photodecomposition of volatile organic compounds (VOC). We employed a continuous industrially scalable extrusion-based process making the use of hybrid sols of amorphous titania nanoparticles, polyvinyl alcohol (PVA) and occasionally latex nanoparticles. This process allowed for the continuous generation of hybrid TiO2/latex/PVA or TiO2/PVA macroscopic fibers. Upon thermal treatment, biphasic porous fibers are obtained containing the anatase phase of TiO2 with 10-15% of brookite. These fibers, which can be manufactured under several hundred meter of length, are offering significantly improved phototocatalytic efficiency now comparable to the commercial Quartzel®PCO photocatalyst for gas-phase acetone mineralization.