The thiazole-2-imine derivatives with interesting pharmacological activities have attracted significant attention. However, previously reported synthesis strategies usually suffered from some drawbacks, such as the use of metals/additive and harsh reaction conditions. Herein, we developed a metal- and photoinitiator-free photocatalytic strategy for the synthesis of various selenium-substituted thiazole-2-imine derivatives for the first time. The reaction displayed mild reaction conditions, simple operation, a broad substrate scope (37 examples), and good to excellent yields.