• Polymeric ionic liquid bucky gel sorbent coatings were developed for SPME. • Method involved on-fiber co-polymerization by thermal free-radical polymerization. • Sorbent coatings were used for the extraction of polycyclic aromatic hydrocarbons. • Higher partition coefficients resulted from increased loading of carbon nanotubes. • The sorbent coatings were validated by studying recovery from river and tap water.
