Electroactive β phase content of poly(vinylidene fluoride-hexafluoropropylene) (PHP) was enhanced by blending approach with polycarbonate (PC) combined with application of barium titanate–multi-walled carbon nanotubes (BT–MWCNT) hybrid nanofillers to boost the dielectric performance of PHP. The samples were melt-blended at 90/10 and 70/30 wt% (PHP/PC) in the presence of BT and/or MWCNT. Scanning electron microscopic (SEM) results indicated compatibilization of the structure by adding BT or MWCNT; however, the best refinement in morphology was obtained in (90/10)/1.5/1.5 (PHP/PC)/BT/MWCNT nanocomposite. Transmission electron microscopy (TEM) micrographs illustrated the selective localization of BT at PHP and MWCNT at PC while some of both nanofillers were found at the interphase. Fourier transform infrared spectroscopy and X-ray diffraction analysis results depicted the increase in β/α ratio of the nanocomposites with a synergistic effect in (90/10)/1.5/1.5 nanocomposite, attributed to the combined utilization of BT and MWCNT and their selective localization in the PHP/PC immiscible blends. Differential scanning calorimetry analysis substantiated the nucleating effects of BT and MWCNT and consistency with SEM and TEM observations in nanofillers selective localization. The findings of this work suggest that simultaneous introduction of ceramic and conductive nanofillers with their selective localization in PHP/PC blends is efficacious in improving electroactive phase of composites at low filler content.