Among several oil/water emulsion separation technologies, the utilization of nanoparticle‐decorated membranes with diverse functionalities has received considerable attention in recent years, particularly if the antifouling capacity can be improved. In this article, we propose a new membrane based on surface‐hydrolyzed polyacrylonitrile electrospun membranes and/or decorated with amine‐functionalized Si‐MCM‐41 nanoparticles to be used as oil/water emulsion separation treatment and to determine their antifouling ability. X‐Ray photoelectron spectrometry, attenuated total reflectance Fourier transform infrared spectroscopy, and toluidine blue O assay, scanning electron microscopy, contact angle measurements for oil under water and thermogravimetry were used for characterizing the membranes and an assay of permeability was developed to quantify the diffusion of oil molecules across the electrospun membrane. The electrospun and/or decorated membranes showed an underwater oleophobic wettability, which can separate oil‐in‐water emulsions with 87% separation efficiency, results of fouling experiments, evaluated in terms of rejection and flux recovery ratio, exhibited good antifouling ability, but the membrane decoration process did not lead to superior outcomes compared with undecorated membranes.