Unnatural amino acids (UAAs) are highly valuable building blocks in organic synthesis, pharmaceuticals, and material sciences. Previously, we developed the LADA strategy for the synthesis of UAAs. Herein, we further expanded the scope of this strategy to alkenylboronic acids. Interestingly, both photoinduced single-electron transfer (SET) and energy transfer (EnT) processes were involved in this reaction, and the E/Z ratio of the products could be changed upon reaction condition.