Two-phase cooling has become a promising method for improving the sustainability and efficiency of high energy-density and power-density devices. Fundamentally, however, two-phase thermal transport is not well understood for local, transient processes, especially at critical to near-critical heat fluxes at the macro, micro, and nano-scales. Here we report spatiotemporal characterization of the single-bubble ebullition cycle in a hot-spot heating configuration with heat fluxes approaching 3 kW cm −2 . In particular, we experimentally reconstruct the spatiotemporal heat transfer coefficient in terms of its proportionality at both the macro-scale (l >> 1 μm) and the micro-to-nanoscale (l < 1 μm). We show that the maximum rates of heat transfer occur during the microlayer evaporation stage of the ebullition cycle, corresponding to critical maxima in the heat transfer coefficient of~160 ± 40 kW m −2 K −1 and~5300 ± 300 kW m −2 K −1 at the macro-scale and micro-to-nanoscale, respectively.