Semiflexible liquid crystalline polymers based on Schiff bases as mesogenic cores have been synthesized through different synthetic strategies. The mesogenic cores are derived from 1,5-naphthalenediamine linked to a polymethylenic spacer by means of ether or ester groups. The synthetic strategies differ in the disconnection of the molecules to design the synthesis of the repeating units. Polymers were synthesized either as polyazomethines, where imine bonds are formed in the polymer synthesis, or as polyethers or polyesters, where the ether or ester groups are formed at the polymer-forming stage. The influence of the synthetic method and the linking groups between mesogenic core and flexible spacer on the thermal and mesogenic properties has been analyzed by DSC, thermogravimetry, and optical microscopy. The possibility of obtaining hydroxy-functionalized polymers by different synthetic strategies has been studied as well as the influence of these groups on the thermal and mesogenic properties.