Microwave gas monitoring with a low‐profile design and enhanced selectivity remains a persistent challenge. This study introduces an innovative approach employing a real‐time wireless reconfigurable intelligent surface (RIS) for comparative investigation of the interaction of two distinct polydimethylsiloxane (PDMS) interfaces, i.e., solid and porous, with acetone gas molecules. The developed PDMS‐coated microwave RIS detects varying concentrations of acetone vapor by wirelessly monitoring variations in the resonant characteristics of the resonating RIS beneath the sensitive interface. This PDMS‐coated microwave RIS is validated through exposure to incremental (15–75) parts per thousand (ppt) acetone concentrations and demonstrated a sensitivity of ≈4.4 MHz/ppt and ≈4.3 MHz/ppt of acetone for solid and porous PDMS, respectively. Integrating PDMS and microwave‐based RIS systems provides a sensitive tool for tracking the interaction of acetone gas and PDMS and demonstrates this system's capability for sensitive gas detection. This study introduces a unique development in the wireless detection of VOCs and presents a compact and passive approach with enhanced sensitivity, making it suitable for monitoring the interaction of polymers and hazardous VOCs. This technology is particularly suited for use in challenging and hard‐to‐reach environments.