In the last three decades, smart materials have become popular. The piezoelectric materials have shown key characteristics for engineering applications, such as in sensors and actuators for industrial use. Because of their excellent mechanical-to-electrical and vice versa energy conversion properties, piezoelectric materials with high piezoelectric charge and voltage coefficient have been tested in renewable energy applications. The fundamental component of the energy harvester is the piezoelectric material, which, when subjected to mechanical vibrations or applied stress, induces the displaced ions in the material and results in a net electric charge due to the dipole moment of the unit cell. This phenomenon builds an electric potential across the material. In this review article, a detailed study focused on the piezoelectric energy harvesters (PEH’s) is reported. In addition, the fundamental idea about piezoelectric materials, along with their modeling for various applications, are detailed systematically. Then a summary of previous studies based on PEH’s other applications is listed, considering the technical aspects and methodologies. A discussion has been provided as a critical review of current challenges in this field. As a result, this review can provide a guideline for the scholars who want to use PEH’s for their research.