The temperature and frequency dependent dielectric relaxation behavior of a liquid crystalline (S)-(+)-1-methylheptyl 4-[2-(4-alkoxyphenyl) thiophene-5-carbonylthiooxy] benzoate system is reported. Interesting successive antiferroelectric-ferroelectric-antiferroelectric (AF-FE-AF) phase transitions are observed in this system resembling the successive phase transitions observed in crystalline Rochelle salt. The smectic-C*(SmC*) to AF1 phase transition (around 103.0 °C) is first order in nature, predicted from the use of Orihara and Ishibashi theory. It is also found that a contribution of the ferroelectric SmC* phase ordering penetrates even in the antiferroelectric AF1 (SmCA*) and AF2 (SmCA*) phases very close to the SmC*-AF1 and SmC*-AF2 phase boundaries (critical regions). It is suggested that this type of mixing of AF and FE phases might cause surface induced ferroelectric- or ferroelectric-type ordering near the AF-FE phase transitions. A soft mode with Debye-type dispersion was observed in the SmA phase. The thermal behaviors of dielectric dispersion, absorption, and dielectric strength in different phases are also reported and discussed.