We demonstrate the real-time tracking of explosive boiling dynamics at the alcohol/MXene interface by monitoring the photoinduced lattice dynamics of MXene nanosheets dispersed in different alcohols. As revealed by ultrafast spectroscopy, the explosive boiling experiences three cascading stages, i.e., the starting initiation (0-1 ns), the following phase explosion (1-6 ns), and the eventual termination (>6 ns). More importantly, the occurrence conditions of explosive boiling are rationally evaluated via photothermal modeling, echoing well to our experimental observations and further suggesting that ∼17-25 layers of alcohol molecules undergo phase transition from liquid to vapor, a result that can hardly be attained by other physicochemical means. Additionally, useful insights into thermal conduction/diffusion and transient acoustic pressure related to the early stage of explosive boiling are provided. This paradigmatic study enriches the fundamental understanding (on a microscopic level) about the elusive dynamics of explosive boiling at the liquid-solid interface.