An asymmetric siloxane is made by reacting a silicone having the formula M.sup.HD.sub.xM'.sup.H where M.sup.H is R.sup.1R.sup.2HSiO.sub.1/2, M'.sup.H is R.sup.4R.sup.5HSiO.sub.1/2 and x is an integer 0.ltoreq.x.ltoreq.10 under selective hydrosilylation conditions in the presence of a precious metal hydrosilylation catalyst, with a first olefinic compound and in a second step, a monohydridosiloxane produced in the first step is reacted under hydrosilylating conditions with another olefinic compound different from the first olefinic compound.