Increasing demand for oil and gas leads to the generation of substantial amount of produced water, bringing about deleterious impacts on the environment. Direct-contact membrane distillation (DCMD) could be a possible option for dewatering oil-in-water (O/W) emulsions because of many benefits brought by the DCMD process. However, these low surface tension solutions pose some difficult issues such as membrane fouling and pore wetting. The mechanisms involved are not fully understood due to the lack of study of the interaction between the emulsions and the membrane surface in the DCMD domain. To address the challenges, this study aims at developing a fundamental understanding of the relationship between surfactant-stabilized O/W emulsions and polyvinylidene fluoride (PVDF) membrane surface in DCMD operations. Effects of surfactant types (Span 20, Tween 20, and sodium dodecyl sulfate), oil concentration, and oil types (petroleum and vacuum pump oil) were systematically studied to better understand the fouling and wetting mechanisms involved. The results reveal that surfactant concentration and hydrophobicity had an influence on the membrane fouling and wetting behaviors. Surfactants with a lower hydrophilic-lipophilic balance (HLB) value could make the PVDF membrane surface less hydrophobic and cause less severe fouling by restraining the adsorption of oil droplets on the membrane surface. These findings suggest that membrane surface modification is required to achieve anti-fouling and anti-wetting properties to make DCMD an energy-efficient and effective technology for treating produced water.