Bioelectrical phenomenon in natural bone has been recognized for its role in bone development and fracture healing. For example, the piezoelectricity induced electro-microenvironment assists in repair and regeneration of bone tissue. The concept of piezoelectricity induced osteogenesis has driven the development of piezoelectric bone mimicking implants. Against this backdrop, we review here the origin of dielectric and electrical response such as piezo-, pyro- and ferroelectricity of natural bone along with their consequences in regulating the bone metabolic activities. The challenging problem of processing the compositionally tailored perovskite biocomposites and its consequence on structural changes, leading to a spectrum of functional properties, are emphasized. A number of recent studies have been compiled to demonstrate the positive impact of piezoelectricity and/or electrical stimulation on cell proliferation, tissue regeneration, cancer treatment etc., in a range of piezoelectric bioceramics, including sodium potassium niobate, barium titanate, magnesium silicate, lithium niobate, zinc oxide, boron nitride etc. and various piezoelectric biopolymers such as, polyvinylidene fluoride (PVDF), poly-L-lactic acid (PLLA), polyhydroxybutyrate (PHB), polyamides (Nylons, peptides etc.), polysaccharides (cellulose, chitosan etc.) and collagen etc., in vitro/ in vivo. It has also been elaborately discussed as how the polarization/ electric field stimulation together with substrate functional properties can synergistically modulate cell functionality. Taken together, this review comprehensively emphasizes the appealing relevance of piezo-bioceramics and piezo-biopolymers as next generation orthopedic biomaterials.