Ethenesulfonyl fluoride (ESF) is a versatile molecule that has attracted attention in synthetic and medicinal chemistry due to its unique reactivity. In this study, we investigate Rh(III)-catalyzed C–H functionalization reactions using ESF as a coupling partner for the modification of heteroaromatic scaffolds frequently found in natural products. The current work focuses on substrates such as chromones, xanthones, and naphthoquinones, which are widely present in biologically active natural compounds. After establishing optimized reaction conditions, substrate scope studies are currently being conducted to evaluate the generality of the transformation. The resulting vinyl sulfonyl fluoride products are expected to serve as useful intermediates for further diversification through SuFEx-based transformations, providing opportunities to access structurally diverse molecules from readily available natural product–derived scaffolds. In addition, this strategy is expected to be applicable to a broader range of natural product frameworks, including flavones, isoflavones, and chalcones. Through this approach, we aim to develop a synthetic tool that enables the generation of structurally diverse derivatives for biological evaluation. Ultimately, this work seeks to identify bioactive molecules and further expand toward the optimization of biologically active derivatives.