Here, in this paper, we have reported the structural, microstructural, optical, ferroelectric and magnetic properties of Nd and W/Co co-substituted Bi4NdTi3−2x(W/Co2)xFeO15 (0.00 ≤ x ≤ 0.15) 4-layered Aurivillius multiferroic ceramics. These ceramics were prepared by conventional high-temperature solid-state reaction method. The room temperature (RT) X-ray diffraction (XRD) and Raman studies revealed that, these ceramics exhibits a pure orthorhombic structure with A21am space group. The surface morphology of these ceramic studies confirmed the formation of randomly oriented grains as non-uniform in size. Further, W/Co2 substitution in BNFT revealed the presence of asymmetrical shaped internal nano-size domains. The band gap of the ceramics was calculated and found to be decreased upon with increasing the concentration of W/Co2. All compounds exhibited improved P–E loops with unsaturated polarization upon substitution with enhance polarization and reduced coercive field. It was found that with higher substitution levels x ≥ 0.10 adversely affected the ferroelectric characteristics. The magnetic measurement revealed that Nd and W/Co co-substitution induced a strong ferromagnetic interaction via Fe3+–O–Co2+/3+ coupling. The high-temperature magnetization studies revealed the Curie temperature (TC) enhances as the W/Co2 concentration increase. Henceforth, the observed outcomes are emphasized for designing new single-phase room temperature multiferroics in future magnetoelectric applications. © 2019, Springer Science+Business Media, LLC, part of Springer Nature.