Abstract: Unsaturated α-amino acids represent an important class of bioactive molecules, which have attracted extensive attention due to their significant application value in the development of various pharmaceuticals. Consequently, numerous efficient approaches for synthesizing such compounds have been developed. Among them, the synthesis of unsaturated α-amino acid derivatives via transition-metal-free catalytic strategies not only offers prominent advantages such as availability of raw materials, environmental benignity, and cost-effectiveness, but also effectively mitigates the potential risk of metal residues during the synthesis of such bioactive molecules. This review summarizes recent advances in the transition-metal-free catalytic synthesis of unsaturated α-amino acid derivatives, with a specific focus on the applications of organophosphorus compound catalysis, nitrogen-containing organic molecule catalysis, and organochalcogen compound catalysis. It is expected to provide synthetic insights for the development of novel bioactive molecules based on these derivatives, particularly for the development of therapeutic agents against high-incidence endemic diseases in the Guangxi Zhuang Autonomous Region.