State-of-the-art commercial membranes are made with the sol-gel method. But the pore size is somewhat restricted to control in a reproducible way. Furthermore, the synthesis of uniform pores via the sol-gel method is challenging, and therefore the resulting membranes often exhibit a limited selectivity. In contrast, the template-assisted method (evaporation-induced self-assembly) described herein is able to form defect-free membranes and thin films with more narrow pore size distributions and thus sharper cutoff curves in a more reproducible way. Moreover, the effect of different templates (Brij 58, Brij 56, Brij 78, Brij 76) and concentrations on the porosity of the titania top layer and separation performance is thoroughly investigated. The pore formation mechanism of the template-assisted method is discussed. Under the synthesis conditions described herein, the Brij templates act as a separator, whereby the final pore size can be easily controlled by adjusting the amount of template used. Furthermore, the pores obtained with this template-assisted method are more uniform. Such defect-free, reproducible small pore ultrafiltration membranes with controllable pore size and narrow pore size distribution can open the path to further process intensification and more sustainable production by separating molecules with a small difference in molecular weight.