A new strategy for highly concise, convergent, and enantioselective access to polydeoxypropionates has been developed. ZACA‐Pd‐catalyzed vinylation was used to prepare smaller deoxypropionate fragments, and then two key sequential Cu‐catalyzed stereocontrolled sp3–sp3 cross‐coupling reactions allowed convergent assembly of smaller building blocks to build‐up long polydeoxypropionate chains with excellent