ABSTRACT In response to the growing demand for efficient synthetic methodologies, we report herein a practical and cost‐effective photochemical decarboxylative allylation protocol, utilizing thioxanthone as an affordable organic photocatalyst under blue‐LED irradiation. This metal‐free approach enables the direct coupling of various carboxylic acids and N ‐protected amino acids, which represent abundant and widely used feedstocks, with Morita–Baylis–Hillman derivatives. The reaction proceeds under mild conditions and has been successfully applied to a broad substrate scope, demonstrating the method's versatility and ability to produce complex multifunctional molecules.