Organopolysiloxanes containing pendent silicon-bonded aminomethylene groups may be prepared by reaction of hydroxy-functional siloxanes or polysiloxanes with aminomethylalkoxysilanes. By adjusting the functionalities of the siloxane and silane, branched siloxanes with aminomethylene functionality may be obtained, as may also organopolysiloxanes of high amine number, reflecting numerous chain-pendent aminomethylene groups. The products are easily emulsifyable in water.