2-(p-hydroxyphenyl)-ethanol (PHPE) and m-hydroxybenzyl alcohol (MHBA) were major components of subfractions of the tumor-promoting fractions of cigarette smoke condensate (CSC). To further investigate the possible role of these and related compounds in tumor promotion and cocarcinogenesis by CSC, an analytical method was developed for hydroxyphenyl ethanols and hydroxybenzyl alcohols in tobacco and tobacco smoke. The method consisted of a series of solvent partitions followed by preparative thin-layer chromatography and gas-liquid chromatography of the silylated hydroxyphenyl alcohol fraction. p-Hydroxybenzyl alcohol (PHBA) was used as internal standard. The main stream smoke of a typical 85-mm U.S. non-filter cigarette contained 3.3±0.3 μg/cig of PHPE and 1.0 ±0.1 μg/cig of MHBA; that from filter cigarettes contained from 1.2-2.8 μg/cig PHPE and 0.28-0.66 μg/cig MHBA. PHPE, but not MHBA was detected in unburned tobacco (0.96-15.0 μg/g). The major source of PHPE in mainstream smoke was apparently transfer from tobacco, while MHBA was formed, at least partially, from cellulose. PHPE levels in cigarette tobacco and smoke were reduced by extraction of the tobacco with the hexane-ethanol azeotrope.