A novel homologous series of 4(4 '-n-alkoxy benzoyloxy)phenylazo 2 ''-chloro-3 ''-methyl benzenes was synthesized and studied for mesophase behavior dependence on molecular structure. The nematogenic mesophase is exhibited from the first to the last member and the smectogenic mesophase from the hexyloxy to the tetradecyloxy member of the series. The nematic mesophase is of a threaded or Schlieren type, and the smectic mesophase is of a focal conic fan of the type A or C. Mesomorphic properties of the present novel homologous series are compared with other structurally similar homologous series.