Optically active expanded chelate phosphines were synthesised by reaction of bromotolyl, bromoxylyl and bromodiphenylmethane derivatives with 1,omega-bis(dichlorophosphino)alkanes. The bromotolyl, bromoxylyl and bromodiphenylmethane ethers were obtained from the corresponding bromo(bromomethyl)arenes and the optically active alcohol (-)-borneol.