Considering the growing environmental concern, there is a dire need to understand the persistence of hydrocarbon-based toxic substances, both in pristine and mix forms, in different matrices. Most of these toxic substances pose hazardous threats directly or indirectly to entire living ecosystems. In this context, the uncontrolled or accidental leakage of petrochemicals and/or trace residues from the oilfields or refinery units are considered a rich source of emerging contaminants with a notable potential to damage the water matrices. Thus, effective treatment with standardized measures is of supreme interest to address the environmental pollution, at large, and water insecurity, in particular. Robust remediation measures should be taken to mitigate or at least lower the environmentally related adverse impacts and human-health related threatening concerns of hydrocarbon-based toxic substances. Several of in practice conventional treatments had been old-fashioned, insufficient, and expensive. Herein, we reviewed metal-organic frameworks (MOFs) based innovative approaches to tackle hydrocarbon-based petroleum source contamination. Metal ion or clusters incorporated in organic ligands leads to the formation of one, two-dimensional (2D) or three-dimensional (3D) hierarchy materials so-called “MOFs”. Besides, the bond flexibility between inorganic (metal) and organic polymers) units, intricate synthesis of MOFs with requisite functionalities for oil/water separation. The selection of accurate metal and organic components for the integration of chemically and thermally stable MOF crystals with high porosity is essential, especially to explain oil/water separation applications. This review spotlights to understand the hierarchical assemblies and structural geometries of MOFs, followed by applications in the separation of oil/water mixtures for a safer environment.