Synthesis, textural characterization, differential scanning calorimetry, and dilatometry studies are carried out on a new homologous series of N-(p-n-alkoxy benzylidene)-p-n-pentyloxy anilines (nO.O5) where n = 1–18. The lower homologues of this series (n = 1–5) and a higher homologue (n = 16) exhibit monotropic Liquid Crystal (LC) phase. The other members of the series show enantiotropic LC phases, while 18O.O5 is a nonliquid crystal. The dilatometric studies on 7O.O5, 10O.O5, 13O.O5 and 16O.O5 reveal the first-order nature of Isotropic to Nematic Phase (IN), Isotropic to Smectic A Phase (IA), Nematic to Smectic C Phase (NC), Smectic A to Smectic B Phase (AB), Smectic C to Smectic B Phase (CB), and Smectic A to Krystal Phase (AK) transitions. The pretransition effects are estimated from dilatometry results. The results are compared with the available data on nO.m compounds.