Abstract: This study successfully constructed a novel cataluminescence (CTL) sensor based on a core-shell nanostructure. By integrating CeO₂ nanoparticle cores with UiO-66 metal-organic framework (MOF) shells, a high-performance CeO₂@UiO-66 composite sensing material was fabricated for efficient diethyl ether detection. The composite was synthesized via a solvothermal method, which enabled uniform growth of UiO-66 shells on spherical CeO₂ cores, resulting in a well-defined core-shell architecture with abundant porosity. This unique structure not only significantly enhanced catalytic activity but also improved the selective recognition capability toward target molecules. Experimental results demonstrated outstanding sensing performance for diethyl ether, including ultrahigh sensitivity (detection limit: 4.4×10⁻⁵ mol·L⁻¹) and excellent selectivity (showing significantly stronger response than over ten common VOCs). Under optimized conditions (detection wavelength: 490 nm, operating temperature: 360℃, carrier gas flow rate: 300 mL·min⁻¹), the CTL intensity exhibited a good linear relationship with diethyl ether concentration (1-40 mmol·L⁻¹, R²=0.9961) along with remarkable reproducibility (1.0% RSD over 11 cycles; 3.51% RSD over 7 days of continuous operation). In practical sample analysis, the spike recovery rates ranged between 95.4%-105.5%, confirming the method's accuracy and practicality. This work not only provides new insights into the application of MOF-based composites in CTL sensing, but also offers an innovative solution for rapid and precise detection of volatile organic compounds.