A method of preparing a composition for forming a release coating is disclosed. The method comprises preparing a reaction product comprising a polyorganohydrogensiloxane compound having cyclic SiH-functional branching groups interconnected by linear polydiorganosiloxane segments (the “branched cyclic polyorganohydrogensiloxane compound”), by combining together (A) a hydroxyl terminated polydiorganosiloxane and (B) a cyclic polyorganohydrogensiloxane, in the presence of (C) a boron containing Lewis acid and a solvent. A release coating composition including the reaction product comprising the branched cyclic polyorganohydrogensiloxane is also disclosed. The reaction product may be combined with or prepared in the presence of a polyorganohydrogensiloxane diluent and stripped of solvent to prepare the composition as a blend of the branched cyclic polyorganohydrogensiloxane and the polyorganohydrogensiloxane diluent for use in solventless-curable compositions.