A fully rollable nanocomposite-based nanogenerator (NCG) is developed by integrating a lead-free piezoelectric hybrid layer with a type of nanofiber-supported silver nanowire (AgNW) network as electrodes. The thin-film nanocomposite is composed of electroactive polyvinylidene fluoride (PVDF) polymer matrix and compositionally modified potassium sodium niobate-based nanoparticles (NPs) with a high piezoelectric coefficient ( d33) of 53 pm/V, which is revealed by the piezoresponse force microscopy measurements. Under periodical agitation at a compressive force of 50 N and 1 Hz, the NCG can steadily render high electric output up to an open-circuit voltage of 18 V and a short-circuit current of 2.6 μA. Of particular importance is the decent rollability of the NCG, as indicated by the negligible decay in the electric output after it being repeatedly rolled around a gel pen for 200 cycles. Besides, the biocompatible NCG can potentially be used to scavenge biomechanical energy from low-frequency human motions, as demonstrated by the scenarios of walking and elbow joint movement. These results rationally expand the feasibility of the developed NCG toward applications in lightweight, diminutive, and multifunctional rollable or wearable electronic devices.