Inspired by mussels' byssus with remarkable adhesive power that is neither degraded nor deformed in the marine environment, dopamine coating has emerged as an option for membrane surface modification. With its many advantages, direct-contact membrane distillation (DCMD) appears to hold potential for the recovery of high quality water from produced water. However, membrane fouling and pore wetting are challenging issues of long-term DCMD operations due to the presence of oils and surfactants in these waters. Hence, it is paramount to develop robust membranes with anti-fouling and anti-wetting properties for effective produced water treatment. In this study, we fabricated a composite hollow fiber membrane by single-step co-deposition of polydopamine (PDA)/polyethylenimine (PEI) onto the outer surface of a commercial hydrophobic polyvinylidene fluoride (PVDF) substrate. The successful co-deposition was verified using different characterization techniques. The composite membrane exhibited Janus wettability (Janus membranes have opposing properties at an interface) with its modified outer surface being in-air hydrophilic/underwater superoleophobic for preventing organics adhesion while insuring that unmodified pores beneath the surface remained hydrophobic for vapor transport. The anti-fouling and anti-wetting properties of the modified membrane were investigated via DCMD experiments by feeding a series of low surface tension solutions. In comparison to the pristine PVDF membrane, the modified membrane exhibited promising wetting resistant property against different surfactant types and excellent fouling resistant property against nonionic and cationic surfactants. Moreover, the modified membrane presented a promising long-term performance when feeding a cationic surfactant-stabilized petroleum-in-water emulsion mimicking produced water, during which a stable flux and excellent permeate quality were maintained throughout 7 days of operation. The efficacious combined effects of a hydration layer and protonated amine-functional groups on the PDA/PEI grafted layer could prevent membrane fouling and pore wetting. The results suggest that the mussel-inspired composite PVDF membrane could potentially be used for long-term water recovery from produced water via DCMD.