Herein, the effect of cerium substitution on the structural, dielectric, optical, impedance and leakage current characteristics of Nd modified triple layered Aurivillius phase compound of chemical composition Bi3NdTi3-xCexO12 is investigated. The polycrystalline samples are synthesized via ceramic fabrication technology. Room temperature X-ray analysis confirms their orthorhombic symmetry. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) analysis affirm microstructure and elemental composition of the compounds. The temperature-dependent dielectric study indicates diffused phase transition (DPT) behavior possibly induced by compositional fluctuations and random occupancy of equivalent crystallographic sites. Signature peaks pertaining to metal-oxide bond vibrations are also identified by FTIR study. Impedance spectroscopic study unravels negative temperature coefficient of resistance (NTCR) and non-Debye type relaxation in the samples. UV–Visible spectroscopy reveals a reduction in band-gap from 3.1 eV to 2.83 eV with cerium infusion from x = 0 to x = 0.3. It is due to the introduction of localized mid-gap states thus, suggesting the possibility of photovoltaic applications. Further analysis of electric modulus and impedance characteristics propounds prominent short-range carrier hopping with higher cerium percentage. The room temperature I–V study suggests an increase in the voltage-dependent non-linearity with cerium incorporation. Leakage current analysis reveals a transition from Ohmic to space charge limited conduction (SCLC) type behavior with high electric field. Room temperature polarization study confirms their ferroelectric property. Frequency dependent ac conductivity obeys Jonscher double power law clearly indicating the presence of two dispersive regions dominated by grain and grain boundary effects. Reduced bandgap, enhanced voltage dependent non-linearity, NTCR type property and saturated P-E loops observed in the sample unravel the multifunctional aspects of the fabricated compound.