Three series of dibenzo[a,c]phenazines were prepared in an order to assess the impact of side chain position on the phase stability of columnar liquid crystals. Each series was composed of four isomeric compounds differing only in the disposition of hexyloxy and decyloxy chains around the central aromatic core, giving rise to electronically similar compounds with varying shapes and symmetries. The substitution pattern was found to have a moderate effect on the clearing transition of the liquid crystal but a larger impact on the melting temperatures. These observations suggest a viable strategy for controlling the phase range of liquid crystals via judicious choice of peripheral chain structure and location.