Enhancement of power harvesting efficiency in piezoelectric energy harvesters through a non-linear electronic interfacing circuit is a well-established research area with potentially significant implications on piezoelectric energy harvesting efficiency. Among various types of synchronous switching circuits available in the literature, a self-powered electronic breaker is widely studied. Nonetheless, due to the interdisciplinary nature of this field, many of the currently available analyses tend to overlook and/or simplify certain aspects of this dynamical system. As a result, a comprehensive model of the system that considers accurate coupling effect of the interfacing and storage circuitry, as well as detailed analysis of the system during transient capacitor charging and energy harvesting operation is still missing. This paper thus aims at the problem of modeling a piezoelectric energy harvester with an Synchronized Switch Harvesting on Inductor (SSHI) circuit and a self-powered electronic breaker. A semi-analytic numerical model is proposed that is able to accurately simulate the operation of the system during transient process of charging an external storage device. Experiment validation confirms the accuracy of the proposed model considering the exact electromechanical coupling effect and transient charging dynamics with SSHI circuit and the model’s performance in estimating system transient behavior. Furthermore, a systematic parametric study is performed in order to analyze the effects of different system components on the energy harvesting efficiency during transient operation.