The occurrence of ferroelelectric phases and influence of chemical moieties in the area of supra-molecular achiral Bent core Liquid Crystals (BLCs) are reviewed. Synthesis of an intermediate/higher homolog of PBnOB series (for n=11), PBUOB, viz. 1,3−Phenyline-Bis(4−UndecylOxy Benzoate), is presented. Smectic LC phases exhibited by PBUOB are characterized by Polarized Optical Microscopy (POM), Differential Scanning Calorimetry (DSC) and Spontaneous Polarization ( P S) techniques. Observations infer a bi-variant FE LC smectic phase occurrence, viz., isotropic→B 2(FE)→B 5(FE)→solid phases in cooling and solid→B 5→isotropic phases in heating scans. Occurrence of B 2 phase is monotropic (in cooling), while B 5 phase is enantiotropic. I–B 2 and B 2–B 5 phase transitions are found to be of first order nature. The FE phases possess a moderate P S value of ∼40 nC cm −2. Transition temperatures from dielectric studies agree with those from TM and DSC. Two modes of relaxations are observed, viz., a slow scissor mode at ∼1 kHz and a fast mode at ∼1 MHz. Anisotropic Dipolar Model is proposed to explain the reorientation mechanism. Arrhenius shifts of Relaxation Frequency ( f R) show differing activation energies for two modes, i.e., 0.11 and 0.98 eV; 0.25 and 1.18 eV in B 2 and B 5 phases, respectively. Temperature variation of dielectric increment Δ ε and α-parameter LC phases reveals the relative fixture of dipole moment in polar smectic layers. An analytical study for the thermal stability, P S and f R in the FE phases is presented with respect to the constitution and configuration of moieties in BLCs.