Heteroatom-centered radicals show versatile reactivity and offer useful synthetic methods in organic chemistry. The development of new approaches for forming heteroatom-centered radicals has recently expanded the practicality of radical chemistry for synthesis. This review focuses on recent advances in reactions of representative heteroatom-centered radicals.1 Introduction2 Group 17 Elements: Chlorine and Bromine Radicals3 Group 15 and Group 16 Elements3.1 Nitrogen- and Oxygen-Centered Radicals3.2 Phosphorus- and Sulfur-Centered Radicals3.3 Other Radicals4 Group 14 Elements: Silicon-Centered Radicals5 Group 13 Elements: Boron-Centered Radicals6 Conclusion