Three azine oligomeric esters were synthesized, characterized by IR, UV, 1H, 13C{1H} and GPC technique, and applied to chemosensor application. The sensitivity response of the oligomers towards the metal ion was evaluated for a metal ion series. The results have shown selective and sensitive “turn off” fluorescence response towards Fe3+ ion in DMF/H2O (1:1, pH: 7.4, fluorophore: 5 μM) solution. The binding stoichiometry and binding constant of the fluorophores were calculated using the Stern–Volmer equation and Benesi–Hildebrand plots, respectively. The quenching of fluorophores on the addition of Fe3+ ion indicates the capability of fluorophore towards quantitative analysis of Fe3+. The dimer of oligomers was theoretically studied using DFT, B3LYP/6-311G level basic set to support and explain the quenching mechanism of LMCT, PET process and to explain the DC, AC electrical studies results. The electrical conductivity measurements of solid-state, I2 doped and undoped oligomers were carried out and the conductivity gradually increases with increase in iodine vapor contact time of oligomers. The electrical conductivity was related with band gap and charge density values of imine nitrogen obtained by Huckel calculations. The dielectric measurements at different temperatures and frequencies were made by two probe method. Among the oligomers, EBHAP has recorded a high dielectric constant at the low applied frequency of 50 Hz at 373 K due to loosely attached π bonds resulting good polarization.