Polymers and papers, which exhibit piezoelectricity, find a wide range of applications in the industry. Ever since the discovery of PVDF, piezo polymers and papers have been widely used for sensor and actuator design. The direct piezoelectric effect has been used for sensor design, whereas the inverse piezoelectric effect has been applied for actuator design. Piezo polymers and papers have the advantages of mechanical flexibility, lower fabrication cost and faster processing over commonly used piezoelectric materials, such as PZT, BaTiO3. In addition, many polymer and paper materials are considered biocompatible and can be used in bio applications. In the last 20 years, heterostructural materials, such as polymer composites and hybrid paper, have received a lot of attention since they combine the flexibility of polymer or paper, and excellent pyroelectric and piezoelectric properties of ceramics. This paper gives an overview of piezoelectric polymers and papers based on their operating principle. Main categories of piezoelectric polymers and papers are discussed with a focus on their materials and fabrication techniques. Applications of piezoelectric polymers and papers in different areas are also presented.