In this paper, pool boiling of ethanol at atmospheric pressure was analyzed. The enhanced surfaces were made of copper, on which grooves with a depth ranging from 0.2 to 0.5 mm were milled in parallel. The widths of the microchannels and the distances between them were 0.2 mm, 0.3 mm and 0.4 mm, respectively. The highest heat transfer coefficient, 90.3 kW/m2K, was obtained for the surface with a microchannel depth of 0.5 mm and a width of 0.2 mm. The maximum heat flux was 1035 kW/m2. For the analyzed surfaces, the maximum heat flux increase of two and a half times was obtained, while the heat transfer coefficient increased three-fold in relation to the smooth surface. In the given range of heat flux 21.2–1035 kW/m2, the impact of geometric parameters on the heat transfer process was presented. The diameters of the departing bubbles were determined experimentally with the use of a high-speed camera. A simplified model was proposed to determine the diameter of the departure bubble for the studied surfaces.