Development of affordable sorbents for solid phase extraction (SPE) in petroleum fingerprinting analysis is crucial in petroleum and petrochemical industries due to energy demand. In this paper, composite fibre based on expanded polystyrene and zeolite was nanostructured to nanoporous fibre with Type II + IV classification and superhydrophobic-superoleophilic properties. The potential of this composite fibre as SPE sorbent in petroleum fingerprinting was investigated and its efficiency was compared with commercial sorbents [alumina, silica and alumina/silica (hybrid)] cartridges. The chromatograms showed that the packed electrospun composite fibre demonstrated excellent cleaning and enrichment properties for SPE applications relative to the hybrid cartridges. This presents a novel re-use pathway for expanded polystyrene, promotes fast analysis and cost reduction in petroleum fingerprinting.