In this paper, nonlinear piezoelectric energy harvesting induced by a Duffing oscillator is studied, and the bifurcation trees of period-1 motions to chaos for such a piezoelectric energy-harvesting system are obtained analytically. Distributed-parameter electromechanical modeling of a piezoelectric energy harvester is presented first, and the electromechanically coupled circuit equation excited by infinitely many vibration modes is developed. The governing electromechanical equations are reduced to ordinary differential equations in modal coordinates, and eventually an infinite set of algebraic equations is obtained for the complex modal vibration responses and the complex voltage responses of the energy harvester beam. One single mode case is considered in this paper, and periodic motions with bifurcation trees are obtained through an implicit discrete mapping method. The frequency-amplitude characteristics of periodic motions are obtained for the nonlinear piezoelectric energy-harvesting systems, which provide a better understanding of where and how to achieve the best energy harvesting. This study describes about how the nonlinear oscillator induces piezoelectric energy harvesting through a beam system. The nonlinear piezoelectric energy harvesting is presented through a nonlinear oscillator. Due to the nonlinear oscillator, chaotic piezoelectric energy-harvesting states can get more energy compared to the linear piezoelectric energy-harvesting system.