Metastable nanostructures are kinetically trapped in local energy minima featuring intriguing surface and material properties. To unleash their potential, there is a need for non-equilibrium processes capable of stabilizing a large range of crystal phases outside thermodynamic equilibrium conditions by closely and flexibly controlling atomic reactant composition, spatial temperature distribution and residence time. Here, the capture of metastable pseudo-binary metal oxides at room temperature is demonstrated with scalable combustion-aerosol processes. By a combination of X-ray diffraction, electron microscopy and on-line flame characterization, the occurrence of metastable CoCu2O3 is investigated with controlled crystal size (4-16nm) over thermodynamically stable CuO and Co3O4. Immediate practical impact is demonstrated by exceptional sensing and stable catalytic performance for air pollutant detection (e.g., 15 parts-per-billion benzene) shown for, at least, 21 days. This approach can be extended to various binary, ternary and high entropy oxides with even more components. Also, secondary phases can be loaded on such metastable nanocrystals to access novel materials promising for actuators, energy storage or solar cells.