We have developed the double ortho-lithiation of a (diethylamino)diphenylphosphine oxide and tert-butyldiphenylphosphine oxide. The resulting doubly lithiated species can be converted to various ortho-difunctionalized products as well as phosphorus heterocycles, such as dibenzophospholes and 9-phospha-10-metalla-9,10-dihydroanthracene derivatives. The structure and photophysical properties of the prepared 9-phospha-10-sila-9,10-dihydroanthracene derivative were also studied.