The present work explores improved pathways for producing heterotelechelic homo polymers, and A-B or A-B-A type block copolymers. These contain as soft segment polydimethylsiloxane (PDMS) and a harder segment of poly(propylene glycol), or poly(ethylene glycol) (PPG, PEG). The products were obtained via ring-opening polymerization, hydrosilylation and metathesis reactions, all of high significance in industry. These methodologies open new ways for the preparation of materials with improved properties, fostering the various applications of polymers containing PDMS.