BaTiO3 nanofibers (BT NFs), prepared by electrospinning, were used as a filler for electrospun poly(vinylidene fluoride‐co‐trifluoroethylene) (PVDF‐TrFE) nanocomposite mats. The phase structure and the effect of poling conditions on the piezoelectric properties of PVDF‐TrFE/BT nanocomposites were investigated. The results showed an improved degree of crystallinity (78.6%) and a high β‐crystal phase (up to 98.3%) in all electrospun samples, independent of the nanofiber content. The two‐step poling method, applying electric fields of opposite polarity, led to significantly improved piezoelectric constants d33 (−31.7 pC N−1), strongly dependent on the added BaTiO3 nanofibers. The inclusion of piezoelectric ceramic nanofibers into a polymer matrix, easily carried out by means of electrospinning, followed by an ad hoc optimized poling treatment, allowed to develop flexible materials with enhanced piezoelectric properties, potentially exploitable in innovative conversion systems used in wearable and sensing devices.