Piezoelectric polymers, especially poly(vinylidene fluoride) (PVDF) are increasingly receiving interest as smart biomaterials for tissue engineering, energy harvesting, microfluidic, actuator, and biosensor applications. Despite possessing the greatest piezoelectric coefficients among all piezoelectric polymers, it is often desirable to increase the electrical outputs from PVDF for several of these applications. Blending with intrinsically conducting polymers (CP) in the form of nanofiber membranes is one of the facile methods to achieve the same. However, these polymers and their composites have so far been primarily investigated only for their physical property enhancements and in applications like energy storage while their biomedical applications and comparative assessment of their biocompatibility properties have not been yet explored. In this report, electrospinning of PVDF blends with polypyrrole (PPy), polyaniline (PANI), and a modified PANI with l‐glutamic acid (PANI‐LGA/P‐LGA) is performed to obtain different electrically active material membranes. The PVDF:CP composite nanofibers are compared with respect to their nanostructures, β‐phase content, and electrical conductivity. Further, biocompatibility of all the membranes was compared. It was found that incorporation of PPy, PANI, and P‐LGA increased the electrical conductivity of PVDF while the β‐phase content was also substantially enhanced. The highest biocompatibility with a pre‐osteoblast cell line (MC3T3) was exhibited in the order p‐LGA/PVDF > PANI/PVDF > PPy/PVDF, all being significantly higher than PVDF (p < .001). Although P‐LGA/PVDF showed higher electrical conductivity, biocompatibility with MC3T3, it was found to be highly cytotoxic to a HeLa (cancer) cell line. It is concluded that such structure property relations would help in selection of materials for specific biomaterial applications.