Supercapacitors (SCs) are a type of energy storage device with high power density and long lifecycles. They have widespread applications, such as powering electric vehicles and micro scale devices. Working stability is one of the most important properties of SCs, and it is of significant importance to investigate the operational characteristics of SCs working under extreme conditions, particularly during high-g acceleration. In this paper, the failure mechanism of SCs upon high-g impact is thoroughly studied. Through an analysis of the intrinsic reaction mechanism during the high-g impact, a multi-faceted physics model is established. Additionally, a multi-field coupled kinetics simulation of the SC failure during a high-g impact is presented. Experimental tests are conducted that confirm the validity of the proposed model. The key factors of failure, such as discharge currents and discharging levels, are analyzed and discussed. Finally, a possible design is proposed to avoid the failure of SCs upon high-g impact.