Mechanical energy harvesting performances of poly(vinylidene fluoride) (PVDF) based composites are most often correlated with their polar phase and the individual piezoelectricity of the used filler materials. Here we show that the significant enhancement of space charge polarization of the said composites can play the key dominant role in determining their mechanical energy harvesting performance regardless of their polar phase and individual piezoelectricity of the used fillers. For this purpose, ionic liquid has been incorporated into PVDF/0.5(Ba0.7Ca0.3)TiO3-0.5Ba(Ti0.8Zr0.2)O3 (BCZT) composites which led to a huge enhancement in space charge polarization. The gradual addition of ionic liquid into 10 wt% BCZT loaded PVDF (PBCZT) has helped in extraordinarily enhancing the conductivity gradually which has confirmed the huge enhancement of space charge polarization. However, after a certain limit of ionic liquid addition, the polar phase of the composite films is decreased. Despite this, the output voltages from the piezoelectric and piezo-tribo hybrid nanogenerators (PENGs and HNGs, respectively) fabricated by using the developed films have been found to be increased gradually with the increase in the ionic liquid amount in PBCZT composite. As the amount of BCZT filler was kept fixed for all the films, this result has confirmed the key role of space charge polarization of PVDF-based composites in determining their mechanical energy harvesting performances compared to the effect of polar phase and individual piezoelectricity of filler. The optimized PENG and HNG devices have shown the output voltage as high as 52 and 167 V, respectively, with power densities ~85 and 152 μW/cm2 which predicted their excellent usability in real life energy conversion devices. This work also shows that the effect of extraordinarily enhanced space charge polarization is effective in improving the performance of all types of mechanical energy harvesting devices regardless of their mechanisms (piezoelectric or hybrid).