In this study, we developed composite membranes with a hydrophobic substrate and a hydrophilic top surface using electrospinning to mitigate oil fouling in membrane distillation (MD). The electrospinning approach can be universally applied to any hydrophobic membrane substrate and to ensure the non-wetting condition of the substrate due to the electrospun fibrous structure. Using this approach, polytetrafluoroethylene (PTFE) hydrophobic substrate was coated with two different hydrophilic fibrous networks, including a cellulose acetate (CA) fibrous network and a nanocomposite fibrous network comprising CA and silica nanoparticles (SiNPs). We characterized the pristine and the modified membranes using contact angle measurements and tensiometer-based oil probe force spectroscopy, and tested the anti-fouling performance of the different membranes in MD experiments using a saline crude-oil emulsion as the feed solution. While both coatings offered significant improvement in oil fouling resistance compared to the substrate PTFE membrane, the nanocomposite CA-SiNPs fibrous coating outperformed the CA coating in terms of hydrophilicity, oil adhesion resistance, and anti-oil-fouling performance in MD experiments.