Chiral racemic 1,8-bis(tert-butylphenylphosphino)naphthalene oxide (2a) was resolved into enantiomers by fractional crystallization of its diastereomeric adducts 3a with (+)-(2S,3S)-di-O-benzoyl tartaric acid (DBTA), followed by neutralization. Racemic 1,8-bis(tert-butylphenylphosphino)naphthalene (1a) was oxidized with sulfur to two isomers of 1,8-bis(tert-butylphenyl-phosphino)naphthalene monosulfide, rac-4a and rac-4a', or 1,8-bis(tert-butylphenylphosphino)naphthalene disulfide, rac-5a. The compounds were characterized by NMR spectroscopy ( 1 H, 3 1 P, 1 3 C). Crystal structures were determined by the X-ray method for (-)-3a, rac-4a, rac-4a' and rac-5a; this allowed the determination of the absolute configuration (S,S) for the more soluble adduct (-)-3a. It was found that rac-1a undergoes partial epimerization in boiling xylene to give the meso form.