The treatment of triphenylphosphine oxide with organometallic reagents leads to the substitution of up to three phenyl substituents with the incoming carbon nucleophile. The replacement of the phenyl/aryl group in tertiary diarylalkylphosphine oxides or even aryldialkylphosphine oxides was also observed. Naphthyl-substituted phosphine oxides undergo Michael-type addition at the naphthyl group when treated with organolithium reagent.