A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen–carbon dioxide [5% (w/w) H₂/CO₂] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 °C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography–mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or γ-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on γ-alumina were more efficient than a commercial Pd⁰ (5% w/w) on γ-Al₂O₃ formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO₂) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe⁰ formulations.