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This review systematically introduces the pyroelectric effect and evaluation of pyroelectric materials and follows by analyzing and concluding the novel properties corresponding to four kinds of main pyroelectric materials. The emphasis of this review focuses on several significant and practical applications of pyroelectric materials in thermal energy harvesting from the external environment, pyroelectric sensing, and imaging, even some electrochemical applications including hydrogen generation, wastewater treatment, sterilization, and disinfection. Finally, the development direction of pyroelectric materials, potential challenges and opportunities in the future are all discussed and proposed. 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