Abstract Three series of ferroelectric liquid crystals containing a (2S)-2-(6-(4-hydroxybiphenyl-4′-carbonyloxy)-2″-naphthyl)propionate mesogenic group and oligo(oxyethylene) spacers were synthesized. These obtained liquid crystal compounds were characterized by NMR, differential scanning calorimetry (DSC), optical polarized microscopy (POM), and X-ray powder diffraction measurements. Some of these materials containing four phenyl rings of ester cores (i.e. -Ph-Ph-COO-naph-) and chiral heptyl tail exhibited a rich mesomorphic behaviour, a blue phase (BP), a cholesteric phase (Ch), a smectic A (SA), a twist grain boundary A (TGBA), and a chiral smectic C (SC*) phase. Another series containing four phenyl rings of ester cores and chiral butyl and pentyl chain tails revealed only a SA phase and a SC* phase. Moreover, a crystal E phase was observed in the short spacer chain (n = 0 or 1) homologues of three series of compounds. Also, the mesomorphism properties were discussed as a function of spacer units, num...