A new class of liquid polysiloxane materials obtainable from cost-effective commodity precursors allow tailoring a plurality of (multi)—functional properties. The materials are classified in terms of their chemical identity, which comprises Q-type nonorganofunctional, T-type monoorganofunctional and optional D-type diorganofunctional moieties. The T-type organofunctional species within a polymeric MBB can be present in various preferred combinations defined by spatial, stereochemical and compositional factors. The corresponding method of production for the liquid polymeric polysiloxanes involves a scalable, non-hydrolytic acetic anhydride method either in a simple one-step format to create statistically distributed “core-only” hyperbranched poly-alkoxysiloxanes or as a two— or multistep process to create “core-shell” materials.