The ferroelectric-ferromagnetic composites are attracting attention as the new generation multifunctional device applications owing to the strong magnetoelectric coupling due to piezoelectric and magnetostrictive constituents. This study focuses on coupling between the piezoelectric 2/3Pb(Mg1/3Nb2/3)O3-1/3PbTiO3 and the rare earth (RE = La3+ and Eu3+) substituted magnetostrictive cobalt ferrite (CoFe1.97RE0.03O4) composites. The M−H loop and P-E loop measurements confirm the ferromagnetic and ferroelectric nature of the composites, respectively. The well-saturated hysteresis loop suggests the ferromagnetic nature of composites ascribed to the ferromagnetic ferrites. The P-E loop becomes broad as the ferrite concentration increases, owing to the conducting nature of the ferrite. In both sets of composites, the 80:20 composition shows the maximum αME value, which is ∼ 4.104 mV/cm-Oe for 80PMN-PT:20CFLO and ∼ 3.142 mV/cm-Oe for 80PMN-PT:20CFEO at 1 kHz. Besides, at the resonance frequency (fr) the 90:10 compositions show a higher αME, ∼3118 mV/cm-Oe at 288 kHz for 90PMN-PT:10CFLO and ∼ 2580 mV/cm-Oe at 282 kHz for 90PMN-PT:10CFEO. The energy harvesting application is demonstrated by placing the sample atop the rotating AC axial exhaust fan. The 80PMN-PT:20CFLO composite produced the highest peak-to-peak AC voltage (Vpp) of about 4.24 V. The outcomes of this study show that the studied composites can be employed effectively for energy-harvesting applications.