The IV–VI compounds formed from elements of columns IV (Ge, Sn, and Pb) and VI (S, Se, and Te) of the periodic table of elements are among the oldest known semiconducting materials. The most prominent representatives, PbS, PbSe, and PbTe, have been used for more than 100 years for electronic and optoelectronic device applications. The IV‐VI materials are narrow gap semiconductors which exhibit quite different structural, electronic, and optical properties as compared to other semiconductors. This arises from the ten valence electrons per atomic pair in the IV‐VI compounds instead of the eight valence electrons typical for the tetrahedrally bonded group IV, III–V, and II–VI semiconductors. This article overviews fundamental aspects of IV‐VI semiconductors, including their structural, optical and electronic properties, as well as practical aspects such as single crystal growth and band gap engineering. In addition, important applications such as infrared detectors, microdisk lasers, and thermoelectric devices are also discussed.