In contrast to the traditional two-electron reaction mode, organic free radical chemistry has gained significant attention due to its unique reaction properties and potential for development. Despite having been disclosed for over a century, free radical intermediates with their high activity are often perceived as difficult to control and can result in disorderly reactions. This has led to insufficient attention being given to research in this field. Therefore, our research group has been focusing on generating and transforming organic radicals in a controlled manner for many years, resulting in the development of several innovative strategies. Apart from classical carbon-based radicals, we have successfully synthesized and transformed various other heteroatom radicals (e.g., nitrogen, silicon, sulfur, and phosphorus) under photochemical conditions.