The implementation of deterministic design approaches in the presence of uncertainty is an adequate design task. Probabilistic methods are then used in structural design procedures, offering structural safety predictions. In this study, reliability-based analysis of a piezoelectric laminated composite plate subjected to the mechanical loads was investigated, accounting for the epistemic source of uncertainty. Material properties of the plate were considered temperature-dependent. The sophisticated mesh-free finite volume approach was employed to actively control the vibration of the temperature-dependent piezoelectric laminated composite plate through the first-order shear deformation principles. The induced vibration was treated as a non-stationary random process, and the generalized failure index was estimated using the first-passage probability concept by adopting the novel asymptotic sampling technique. The veracity of the suggested model was corroborated by alternate approaches in the literature, comprising the finite element approach. Furthermore, the temperature-dependent piezoelectric laminated composite plate with different ply orientations was considered to assess the safety index variation against changes in the ambient temperature and the laminate stacking orientation. The obtained results revealed that with increasing temperature, the reliability of the composite plate reduced. It was also realized that the reliability index is directly correlated with the piezoelectric voltage.