Boiling heat transfer suffers deteriorations under subatmospheric conditions, which can be attributed to a shortage of viable nucleation sites at declining pressures. In this work, the possibility of enhancing low-pressure saturated boiling of water using a combination of wettability patterning and structural modifications was experimentally explored. The copper test surface, comprised of an array of circular “dimples” (0.3 mm in depth, 0.5 mm in diameter, and 3.0 mm in pitch), was spray-coated by polytetrafluoroethylene (PTFE) coatings so as to form a matching biphilic pattern with the surface cavities. The resulting dimpled biphilic surface showed appreciable heat transfer enhancement—with a maximum 60% increase of the average heat transfer coefficient of nucleate boiling compared with a flat biphilic surface—down to about 9.5 kPa. Further lowering the pressure to 7.8 kPa, however, was found to lead to diminished performance gains. The visualization study of the bubble departure dynamics revealed signs of additional vapor trapping of the hydrophobic-coated cavities, which can induce uninterrupted bubble regeneration with zero waiting time and explain the qualified enhancement of subatmospheric boiling. Thanks to a potential secondary pinning of contact line inside the hydrophobic cavities, incomplete bubble detachment could prevail at somewhat lower pressures than was otherwise possible without the dimple structure, leaving behind significantly more vapor residues. However, the vapor-trapping capacity was found to decrease with pressure, which provided clues with regard to the reduced efficacy of the surface at even lower pressures.