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Herein we report the efficient extraction of aromatic analytes from crude oil and tar balls using multiple cyclodextrin derivatives. The known propensity of the cyclodextrins to bind hydrophobic guests in their hydrophobic interiors enhanced the extraction of aromatic analytes from the oil layer to the aqueous layer, with methyl-β-cyclodextrin and β-cyclodextrin providing the most significant enhancement in extraction efficiencies of aromatic toxicants (69% aromatic toxicants in aqueous layer in the presence of methyl-β-cyclodextrin compared to 47% in cyclodextrin-free solution for tar ball oil extraction), and provide optimal tunability for developing efficient extraction systems. The cyclodextrin derivatives also promoted efficient energy transfer in the aqueous solutions, with up to 86% efficient energy transfer observed in the presence of γ-cyclodextrin compared to 50% in the absence of cyclodextrin for oil spill oil extraction. Together, this dual function extraction followed by detection system has potential in the development of environmental remediation systems.