The present studies have mainly been focused on the development (synthesis and characterization) of eco-friendly co-substituted (Ni, Ti) bismuth ferrite (referred as BFO) multiferroic of a composition Bi(Ni0.35Ti0.35Fe0.30)O3. The structural and morphological features of the ceramic technology prepared material were first examined by powder X-ray diffraction and field-emission scanning electron microscopy (FE-SEM) techniques. It is found that the Fe-site co-substitution has created deformation in structure of BFO from rhombohedral to orthorhombic symmetry. Their crystallite size was estimated by the Scherrer’s technique and found to be in the range of 20–49 nm. Detailed analysis of the FE-SEM micrograph and EDX (energy-dispersive X-rays) spectrum has shown the (i) uniform distribution of grains of varying size and (ii) elemental content and composition of the Bi(Ni0.35Ti0.35Fe0.30)O3 compound. Studies of the dielectric-impedance spectroscopy and transport parameters, obtained in a broad range of temperatures (298–773 K) and frequency (1 kHz–1 MHz), have provided many important data and mechanism, such as dielectric dispersion at high temperature, conduction mechanism, transport properties, non-Debye type of relaxation processes and negative temperature coefficient behavior of resistance (NTCR) of the studied material. The polarization vs. electric field (hysteresis loop) analysis exhibits that the magnitude of polarization increases with the increase of applied electric field. The magnetic measurement shows the change in ferromagnetic properties which may be due to the observed high remanent magnetization and coercive field. Thus, prepared material with modified multiferroic features may lead to numerous applications in the field of transducers, sensors and electronic industry.