A triple-orifice spinneret has been applied for the preparation of hollow fiber microfiltration membranes with a high surface porosity. Considering the general rules of diffusion induced phase separation, a low polymer concentration is required at the outer layer to obtain a highly interconnected open-porous structure. Therefore, by using N-methylpyrrolidone (NMP) as the external liquid at the outside orifice of the spinneret, a highly porous surface can be obtained. For a polymer solution containing a low molecular weight additive and with an initial concentration close to the cloud point, this technique shows slightly improvement on the pure water and gas fluxes since the major resistance of the membrane is located at the substructure and the inner skin. However, for a solution containing a high molecular weight additive and with an initial concentration far from the cloud point, a porous shell surface is obtained, resulting in a significant improvement in water flux. The effect of various external liquids on the morphology has been investigated as well.