The emergence of multiferroic materials particularly bismuth iron oxide (BiFeO3) with distinctive magnetoelectric, and high energy storage capabilities, present pivotal aspects for next-generation memory storage devices. However, intrinsically weak magnetoelectric coupling limits their widespread applications, that can be leap over by the integration of BiFeO3 with enriched ferroelectric, and ferro/ferrimagnetic materials. Here, a series (1 − x)[0.7BiFeO3 + 0.3MnMoO4] + xNiFe2O4 (x = 0.00, 0.03, 0.06, and 0.09) is synthesized via citrate-gel based self-ignition, and solid-state reaction routes. Phase purity and crystallinity of tri-phase composites with surfaces revealing random and arbitrarily shaped grains are assured by X-ray diffraction, and field emission scanning electron microscopy, respectively. Dielectric studies illustrated non-linear trend for broad range of frequencies as predicted by Maxwell–Wagner theory along with single semicircle arcs in Nyquist plots that exposes grain boundaries effect. An enriched 68.42% of ferroelectric efficiency is featured for x = 0.06 substitutional contents, while magnetic computations demonstrated improved saturation magnetization (Ms), remanence magnetization (Mr), and coercive applied magnetic field (Hc) values as 5.87 emu g−1, 0.96 emu g−1, and 215.19 Oe, respectively for x = 0.09 phase-fraction. The intriguing linear trends of magnetoelectric coupling for all the compositions are corroborating them propitious contenders for futuristic multistate devices.