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 (n0.05) where n 1-18. The lower homologues of this series (n1-5) and a higher homologue (n = 16) exhibit monotropic Liquid Crystal (LC) phase. The other members of the series show enantiotropic LC phases, while 180.05 is a nonliquid crystal. The dilatometric studies on 70.05, 100.05, 130.05 and 160.05 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 n0.m compounds.