An innovative approach towards the extraction of highly pure naphthalene crystals was developed using efficient and inexpensive non-chromatographic solvent extraction method from pyrolysis fuel oil (PFO). Self-crystallization of naphthalene was established during the cooling process of extracted liquor. Naphthalene crystals were recrystallized with ethanol and fully characterized by various analytical techniques such as (1)H and (13)C NMR, FT-IR, TGA, GCMS etc. In general, the solvent extraction and self-crystallization techniques were capable of producing accurate data for native naphthalene from PFO. (C) 2011 Elsevier B.V. All rights reserved.