<p>Modulating the molecule adsorption-desorption behaviors of solid catalysts is important for fulfilling complicated catalytic purposes. Herein, we quantitatively reveal the dynamic balancing of molecule adsorption/desorption by curvature modulation on a series of self-pressurizing mesoporous nanoreactors with controlled concave-convex Gaussian curvatures via a programmable nanodroplet buckling strategy. The encapsulation of Fe₃O₄ nanoparticles in the cavity produces a large temperature difference between the nanoreactor surface (193.8 °C) and the reaction medium (73.7 °C) under photoexcitation, forming thermally confined self-pressurizing nanoreactors. Together with the external pressure exerted by the liquid-surface-tension on the concave-convex surfaces, the self-pressurizing drives the dynamic regulation of molecule adsorption-desorption on the Gaussian surface. Based on this, the nanoreactor with catalytic metallic Ru on the outer shells achieves the high-selective cascade oxidation of biomass-derived 5-hydroxymethylfurfural to high-value-added 5-formyl-2-furancarboxylic acid (97.9% selectivity), showing a reaction efficiency that is an order of magnitude higher than that of conventional heating.</p>