This short review covers the most important advances published in the literature during the last five years, concerning the synthesis, chemical modifications, and applications of SF5 and SF4 Cl compounds in medicinal/bioorganic chemistry and materials science. 1 Introduction 2 Methods for Incorporation/Manipulation of SF4 Cl/SF5 Groups 2.1 Nonaromatic SF5 Compounds via Direct Pentafluorosulfanylation of Alkenes and Alkynes 2.2 SF4 Cl- and SF5-Aryl/Heteroaryl Derivatives 3 Synthesis of SF5 /SF4 Cl/SF4-Substituted Small Molecules 3.1 Heterocycles 3.2 Amines and Amino Acids 3.3 α-SF5 ketones 3.4 Miscellaneous Alkyl-, Alkenyl-, and Aryl-SF5 Compounds 4 Medicinal/Biological Applications 4.1 Anticancer Compounds 4.2 Antibacterial and Antiparasitic Compounds 4.3 Central Nervous System 4.4 Miscellaneous Biological Activity 5 Materials Science Applications 6 Conclusion [ABSTRACT FROM AUTHOR]