Magnetocaloric alloy, Gd5Si2Ge2, was developed into a composite with the poly(vinylidene fluoride) (PVDF) piezoelectric polymer. This multifunctional material possesses unique properties that are suitable for energy conversion and harvesting. Experimental approaches include using an arc melting technique to synthesize the Gd5Si2Ge2 (GSG) alloy and the spinning casting method to fabricate the composite. The materials were characterized using various techniques at different length scales. These include atomic force microscopy (AFM), optical microscopy, scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS). The results indicated that the phase transformation of the magnetocaloric material close to its Curie temperature induced a significant increase in power generation in the piezoelectric polymer. The power output of a laminated structure was 1.1 mW, more than 200 thousand times higher than the piezoelectric materials alone (5.1 nW).