Abstract Anhydrous zinc chloride supported in the solid state was found to produce colored intermediates by reactions with aromatics (anthracene, naphthacene, pentacene, pyrene, pelyrene, and chrysene) at 60 °C. The measurements of their electronic absorption spectra and ESR spectra confirmed that these were the same aromatics-zinc chloride σ-complexes and aromatics cation radicals as those formed in molten zinc chloride.