The liquid crystal molecule 3-fluoro-4-(3,4,5-trifluorophenyl)phenyl 2,6-difluoro-4-(trans-5-n-propyl-1,3-dioxane-2-yl)benzoate (DIO) has attracted considerable interest owing to its unique ferroelectric nematic phase and extraordinarily high dielectric constant. To expand the DIO series, novel analogs with 1,3-dioxane units converted to ester units (EST analogs) were synthesized, and their physical properties were characterized. The EST analogs exhibited ferroelectric phases similar to those of the corresponding DIO analogs. Interestingly, an EST analogue featuring a defluorinated benzoate unit exhibited a ferroelectric smectic A phase, despite its smaller longitudinal dipole moment of 6.9 D. This result diverges from the common knowledge that the formation of large longitudinal dipoles is traditionally effective in the emergence of ferroelectric phases. Unlike the DIO series, the EST analogs can be readily obtained without the formation of undesired geometric isomers, which is advantageous for practical applications. The results of this study provide valuable insights into the design of liquid-crystalline materials expressing ferroelectric phases.