Piezoelectric cum ferroelectric (FE) oxides constitute a major proportion of the smart functional materials such as actuators, sensors, transducers, filters, resonators, and microelectromechanical systems (MEMS). Among the wide range of materials, the perovskite structures (ABO3) with ferroelectric properties, such as lead zirconate titanate (Pb(Zr, Ti)O3, PZT), barium titanate (BaTiO3), bismuth ferrite (BiFeO3), sodium bismuth titanate ((Bi1/2Na1/2)TiO3), and their solid solutions, are known to exhibit remarkable piezoelectric properties. However, to realize a wider range of applications and to tailor the physical properties, composites with piezoelectrics as one or more of the functional components were synthesized and tested. Polymer-ceramic hybrid composites offer unique properties to meet today's applications. In addition, multifunctional composites that involve magnetic and ferroelectric functionalities are studied extensively for the rich science involved in understanding the physical properties and a plausible range of applications. A combination of piezoelectric with strong piezomagnetic/magnetostrictive materials to form new multiferroic composites has been studied extensively. In this chapter, the need for lead-free piezoelectrics and polymer-ceramic hybrid composites is discussed. Preliminary studies on multifunctional composites with piezoelectric as one of the phases are discussed. The fundamental understanding of coupling between the phases in both polymer-ceramic and multifunctional composites remains ambiguous and offers a potential scope for further studies and novel applications. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.