Surfaces that entrap air underwater can serve practical applications, such as mitigating cavitation erosion and reducing frictional drag. To achieve this, perfluorinated coatings are exploited that are non-biodegradable and fragile. Thus, coating-free, sustainable, and more robust approaches are desirable. Recently, a microtexture comprising doubly reentrant cavities (DRCs) has been demonstrated to entrap air on immersion in wetting liquids. While this is a promising approach, insights into the effects of surface chemistry, hydrostatic pressure, and cavity dimensions on wetting transitions remain unavailable. In response, we investigated Cassie-to-Wenzel transitions into circular DRCs submerged in water and compared them with cylindrical “simple” cavities (SCs). We found that at low hydrostatic pressures (~50 Pa), DRCs with hydrophilic and hydrophobic make-ups fill within 10⁵ s and 10⁷ s, respectively, while SCs with hydrophilic make-up fill within < 10^-2 s. Under elevated hydrostatic pressure ( 90 kPa), counterintuitively, DRCs with hydrophobic make-up fill dramatically faster than the commensurate SCs. This comprehensive report should provide a rational framework for harnessing microtextures and surface chemistry towards coating-free liquid repellency.