Efficient water harvesting with a robust interface is important for realistic applications. Here, a dual chemically reactive porous polymeric interface is introduced to adopt various bio-inspired interfaces for the direct comparison of their water-harvesting performances using an identical experimental setup. An improved water-harvesting performance (1100 mg cm⁻² h⁻¹) was observed when an edible oil (olive oil)-infused hydrophilic and slippery interface was used, in comparison to a hydrophobic slippery liquid-infused porous surface (SLIPS, 800 mg cm⁻² h⁻¹) and a superhydrophobic interface (250 mg cm⁻² h⁻¹). Furthermore, the strategic physical confinement of the hydrophilic-slippery interface and the specific arrangement of chemically modulated hydrophilic patterns on a hydrophilic-slippery background accelerated the shedding of condensed water droplets from 107 s to only 15 s. Eventually, a physically confined hydrophilic SLIPS with chemically modulated patterns yielded a highly efficient (4400 ± 190 mg cm⁻² h⁻¹) water-harvesting SLIPS.