Surfaces patterned with alternating (binary) superhydrophobic–superhydrophilic regions can be found naturally, offering a bio-inspired template for efficient fluid collection and management technologies. We describe a simple wet-processing, thermal treatment method to produce such patterns, starting with inherently superhydrophobic polysilsesquioxane–silica composite coatings prepared by spray casting nanoparticle dispersions. Such coatings become superhydrophilic after localized thermal treatment by means of laser irradiation or open-air flame exposure. When laser processed, the films are patternable down to ∼100 μm scales. The dispersions consist of hydrophobic fumed silica (HFS) and methylsilsesquioxane resin, which are dispersed in isopropanol and deposited onto various substrates (glass, quartz, aluminum, copper, and stainless steel). The coatings are characterized by advancing, receding, and sessile contact angle measurements before and after thermal treatment to delineate the effects of HFS filler concentration and thermal treatment on coating wettability. SEM, XPS and TGA measurements reveal the effects of thermal treatment on surface chemistry and texture. The thermally induced wettability shift from superhydrophobic to superhydrophilic is interpreted with the Cassie–Baxter wetting theory. Several micropatterned wettability surfaces demonstrate potential in pool boiling heat transfer enhancement, capillarity-driven liquid transport in open surface-tension-confined channels (e.g., lab-on-a-chip), and select surface coating applications relying on wettability gradients. Advantages of the present approach include the inherent stability and inertness of the organosilane-based coatings, which can be applied on many types of surfaces (glass, metals, etc.) with ease. The present method is also scalable to large areas, thus being attractive for industrial coating applications.