The invention relates to the preparation of enantiomerically pure bis-diphenylphosphine oxides in a particularly advantageous manner by (1) reacting an aromatic bromine compound with a diphenylphosphinic chloride in a mixture of tetrahydrofuran and an aromatic hydrocarbon to give a diphenylphosphine oxide, which is isolated from a solution in an aromatic hydrocarbon by adding a saturated aliphatic hydrocarbon; (2) metalating the resulting diphenylphosphine oxide in the 6-position and reacting the metalated diphenylphosphine oxide with iodine at temperatures not less than −25° C. in such a way that a small amount of iodine is always present in excess, giving a 2-iodo-diphenylphosphine oxide; (3) preparing a racemic bis-diphenylphosphine oxide from the resulting 2-iodo-diphenylphosphine oxide using copper and an aromatic hydrocarbon solvent and crystallizing the racemic bis-diphenylphosphine oxide from a solution in an aromatic hydrocarbon; and (4) separating isomers using an enantiomerically pure mono- or dicarboxylic acid to obtain a first enantiomer by crystallization from a solution in an aromatic hydrocarbon and obtaining a second enantiomer by hydrolysis and subsequent crystallization from a solution in an aromatic hydrocarbon.