MIL-53(Al) is a metal-organic framework (MOF) with unique properties, including structural flexibility, thermal stability, and luminescence. Its ability to adsorb volatile organic compounds (VOCs) and water vapor makes it a promising platform for sensing applications. This study investigated the adsorption mechanism of MIL-53(Al) with different VOCs, including ketones, alcohols, aromatics, and water molecules, focusing on structural transformations due to pore size variation and photoluminescence properties. The reported results assess MIL-53(Al) selectivity towards different VOCs and provide insights into their fundamental properties and potential applications in sensing.