In this work, piezoelectric energy harvesting (PEH) performance via friction-induced vibration (FIV) is studied numerically. A nonlinear two-degree-of-freedom friction system (mass-on-belt) with piezoelectric elements, which simultaneously considers the stick-slip motion, model coupling instability, separation, and reattachment between the mass and belt, is proposed. Both complex eigenvalue analyses and transient dynamic analysis of this nonlinear system are carried out. Results show that it is feasible to convert FIV energy to electrical energy when the friction system is operating in the unstable vibration region. There exists a critical friction coefficient (μc) for the system to generate FIV and output visible voltage. The friction coefficient plays a significant role in affecting the dynamics and PEH performance of the friction system. The friction system is able to generate stronger vibration and higher voltage in the case that both the kinetic friction coefficient and static friction coefficient are larger than μc. Moreover, it is seen that the separation behavior between contact pair can result in overestimating or underestimating the vibration magnitude and output voltage amplitude, and the overestimate or underestimate phenomenon is determined by the located range of friction coefficient. Furthermore, it is confirmed that an appropriate value of external resistance is beneficial for the friction system to achieve the highest output voltage. The obtained results will be beneficial for the design of PEH device by means of FIV.