Hybrid systems with immobilized TiO2 within dual-layer hollow fiber membranes are the most promising set-up for photocatalytic applications because they possess advantages in both the degradation and separation processes. The performance of dual-layer hollow fiber membranes may be maximized using a functional material of high performance as the selective layer. This paper reports the influence of polyethyleneglycol (PEG) as a pore forming agent on the structure and performance of dual layer hollow fiber membranes. Titanium dioxide (TiO2) was used as a photocatalyst in the outer layer of dual layer hollow fiber (DLHF) membranes. DLHF membranes were fabricated via a single step co-extrusion technique and characterized in terms of surface roughness, membrane porosity, hydrophilicity, and cross-sectional and surface morphology. Nonylphenol (NP) photocatalytic degradation and filtration were evaluated using a hybrid membrane photoreactor. The experimental results revealed that DLPEG/TIO2 membrane increases the NP solution flux, while decreasing the incidence of membrane fouling and allowing for a smoother and more hydrophilic membrane surface. The findings show that the addition of PEG in the inner layer of DLHF membranes may enhance flux performance in the photocatalytic process. (C) 2016 Elsevier B.V. All rights reserved.