The synthesis of 1,4-difluorobenzo[c]phenanthrene (1,4-DFBcPh) and its putative oxidative metabolites, the angular ring dihydrodiol as well as the series 1 (syn) and series 2 (anti) diol epoxides, are delineated. Wittig condensation of the phosphonium salt derived from 2,5-difluorobenzyl bromide with 2-naphthaldehyde yielded a pair of cis/trans alkenes, that upon photochemical cyclization afforded 1,4-DFBcPh. Correspondingly, use of 6-methoxy-2-naphthaldehyde for the condensation provided 1,4-difluoro-10-methoxybenzo[c]phenanthrene. This compound was elaborated by cleavage of the methoxy group, oxidation to the quinone and subsequent reduction to the dihydrodiol. The diol epoxides were synthesized diastereoselectively from the dihydrodiol. Some highly interesting differences were noted in ¹H NMR spectra of the series 1 diol epoxides of benzo[c]phenanthrene (BcPh) and 1,4-DFBcPh.