Understanding the mechanism of bubble growth is crucial to modeling boiling heat transfer and enabling the development of technological applications, such as energy systems and thermal management processes, which rely on boiling to achieve the high heat fluxes required for their operation. This paper presents analyses of the evaporation of “microlayers”, i.e., ultra-thin layers of liquid present beneath steam bubbles growing at the heated surface in the atmospheric pressure nucleate of boiling water. Evaporation of the microlayer is believed to be a major contributor to the phase change heat transfer, but its evolution, spatio-temporal stability, and impact on macroscale bubble dynamics are still poorly understood. Mass, momentum, and energy transfer in the microlayer are modeled with a lubrication theory approach that accounts for capillary and intermolecular forces and interfacial mass transfer. The model is embodied in a third-order nonlinear film evolution equation, which is solved numerically. Variable wall-temperature boundary conditions are applied at the solid–liquid interface to account for conjugate heat transfer due to evaporative heat loss at the liquid–vapor interface. Predictions obtained with the current approach compare favorably with experimental measurements of microlayer evaporation. By comparing film profiles at a sequence of times into the ebullition cycle of a single bubble, likely values of evaporative heat transfer coefficients were inferred and found to fall within the range of previously reported estimates. The result suggests that the coefficients may not be a constant, as previously assumed, but instead something that varies with time during the ebullition cycle.