A new series of linear–comb and 4-arm star–comb side chain liquid crystalline polymers (Lc-/Sc-SCLCPs) have been synthesized and characterized. The treatment of hydride siloxane-containing terminated liquid crystalline and high 1,2-/1,4- (high vinyl, hv/low vinyl, lv) linear or 4-arm star polybutadienes (L-/S-PBs) was conducted via the methods in combination of living anionic polymerization and “reverse” hydrosilylation to obtain SCLCPs with wide mesomorphic temperature range (ΔT) and narrow polydispersity index (PDI). The possible molecular arrangement model of two analogous hv-/lv-architectures was constructed, that was used to systematically investigate the effects of Lc- and Sc- topological morphology on liquid crystalline (LC) properties and molecular microstructures. SCLCPs exhibited the same smectic A phase around room temperature, but thermal properties were significantly different due to differences of interaction force resulting from different macromolecular side chains packing. Surprisingly, th...