The prevalence of wearable/implantable medical electronics together with the rapid development of the Internet of Medicine Things call for the advancement of biocompatible, reliable, and high-efficiency energy harvesters. However, most current harvesters are based on toxic lead-based piezoelectric materials, raising biological safety concerns. What hinders the application of lead-free piezoelectric energy harvesters (PEHs) is the low power output, where the key challenge lies in obtaining a high piezoelectric voltage constant (g 33 ) and harvesting figure of merit (d 33 × g 33 ). Here, micron pores are introduced into phased boundary engineered high-performance (K, Na)NbO 3based ceramic matrix, resulting in the state-of-the-art g 33 and the highest d 33 × g 33 values of 57.3 × 10 −3 Vm N −1 and 20887 × 10 −15 m 2 N −1 in lead-free piezoceramics, respectively. Concomitantly, ultrahigh energy harvesting performances are obtained in porous ceramic PEHs, with output voltage and power density of 200 V and 11.6 mW cm −2 under instantaneous force impact and an average charging rate of 14.1 µW under high-frequency (1 MHz) ultrasound excitation, far outperforming previously reported PEHs. Porous ceramic PEHs are further developed into wearable and bio-implantable devices for human motion sensing and percutaneous ultrasound power transmission, opening avenues for the design of next-generation eco-friendly WIMEs.