The generation and controlled or uncontrolled release of hydrocarbon-contaminated industrial wastewater effluents to water matrices are a major environmental concern. The contaminated water comes to surface in the form of stable emulsions, which sometimes require different techniques to mitigate or separate effectively. Both the crude emulsions and hydrocarbon-contaminated wastewater effluents contain suspended solids, oil/grease, organic matter, toxic elements, salts, and recalcitrant chemicals. Suitable treatment of crude oil emulsions has been one of the most important challenges due to the complex nature and the substantial amount of generated waste. Moreover, the recovery of oil from waste will help meet the increasing demand for oil and its derivatives. In this context, functional nanostructured materials with smart surfaces and switchable wettability properties have gained increasing attention because of their excellent performance in the separation of oil–water emulsions. Recent improvements in the design, composition, morphology, and fine-tuning of polymeric nanostructured materials have resulted in enhanced demulsification functionalities. Herein, we reviewed the environmental impacts of crude oil emulsions and hydrocarbon-contaminated wastewater effluents. Their effective treatments by smart polymeric nanostructured materials with wettability properties have been stated with suitable examples. The fundamental mechanisms underpinning the efficient separation of oil–water emulsions are discussed with suitable examples along with the future perspectives of smart materials.