Porous membranes based on polydimethylsiloxane fibers with titanium dioxide nanoparticles were developed to be used as photocatalysts. PDMS was chosen as a support for the titania because of its high thermal and chemical resistance to the photodegradative effect of the TiO2. Porous membranes are produced via electrospinning using three different apparatus configurations. The photocatalytic activity analysis shows that the best results are obtained dispersing the titanium oxide on the surface of the polymer using an electrospinning configuration which involves the use of two needles. The membranes produced in this way show a good catalytic activity, even though lower than the one observed for the pure TiO2 nanoparticles. This is caused by the low wettability of the membranes and by the surface area of the oxide being hidden from the polymer.