Synthesis and characterization of new, molecular DDSQ-based compounds functionalized by substituted styrenes (also with heteroatoms) in a stereoselective manner is presented. Additionally, a novel class of vinylene-arylene linear copolymers with double-decker silsesquioxane fragments in the main chain is developed. These molecular and macromolecular compounds were synthesized via efficient and highly stereoselective silylative coupling (and copolycondensation) and cross-metathesis (and ADMET) reactions.