The boiling performance of functionalized hybrid aluminum surfaces was experimentally investigated for water and self-rewetting mixtures of water and 1-butanol. Firstly, microstructured surfaces were produced via chemical etching in hydrochloric acid and the effect of the etching time on the surface morphology was evaluated. An etching time of 5 min was found to result in pitting corrosion and produced weakly hydrophilic microstructured surfaces with many microcavities. Observed cavity-mouth diameters between 3.6 and 32 μm are optimal for efficient nucleation and provided a superior boiling performance. Longer etching times of 10 and 15 min resulted in uniform corrosion and produced superhydrophilic surfaces with a micropeak structure, which lacked microcavities for efficient nucleation. In the second stage, hybrid surfaces combining lower surface energy and a modified surface microstructure were created by hydrophobization of etched aluminum surfaces using a silane agent. Hydrophobized surfaces were found to improve boiling heat transfer and their boiling curves exhibited a significantly lower superheat. Significant heat transfer enhancement was observed for hybrid microcavity surfaces with a low surface energy. These surfaces provided an early transition into nucleate boiling and promoted bubble nucleation. For a hydrophobized microcavity surface, heat transfer coefficients of up to 305 kW m−2 K−1 were recorded and an enhancement of 488% relative to the untreated reference surface was observed. The boiling of self-rewetting fluids on functionalized surfaces was also investigated, but a synergistic effect of developed surfaces and a self-rewetting working fluid was not observed. An improved critical heat flux was only obtained for the untreated surface, while a lower critical heat flux and lower heat transfer coefficients were measured on functionalized surfaces, whose properties were already tailored to promote nucleate boiling.