The synthesis andmesomorphic properties of a new series of 2,4-bis(4'-n-pentyloxybenzoyloxy)- benzylidine-4 ''-n-alkoxyaniline (DC5An) are reported. The molecular structure of compounds was confirmed by FTIR, H-1-NMR, C-13-NMR, mass spectroscopy and elemental analysis. The mesomorphic properties were studied by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) measurements. All compounds of the series exhibit nematic (N) and smectic C (SmC) phases. The first four homologues (DC5A1-DC5A4) display a N mesophase, whereas the highest homologues (DC5A5-DC5A10) exhibit an enantiotropic dimorphism N and SmC phases. The mesomorphic properties of the present series are compared and discussed with other structurally related series.