Accurately assessing potential side effects following botulinum neurotoxin (BoNT) injection remains a formidable challenge. To address this issue, an innovative approach is developed that combines a wearable temperature sensor with a sophisticated volatilomics technique, aimed at facilitating the rapid and convenient prediction of potential physical discomfort related to latrogenic botulism. The investigation identifies five volatile organic compounds (VOCs)—acetone, styrene, ethanol, 2‐pentanone, and n‐butano—as promising markers indicative of BoNT poisoning. Specifically, a handheld breath analyzer, featuring a yttrium stabilized zirconia (YSZ)‐based gas sensor array, alongside a wearable temperature sensor integrated with a bio‐compatible methacrylated gelatin (GelMA) sensing film, are developed to simultaneously monitor breath signal variations and body temperature fluctuations. Preliminary animal testing validates the effectiveness of the integrated approach, achieving an accuracy exceeding 91.2% in early detection of physical discomfort associated with BoNT poisoning. These promising findings represent a significant advancement towards the early identification of BoNT‐related issues, enabling timely intervention and improved management strategies.