Abstract The hydrothiolation of unsaturated carbon–carbon bonds is a practical and atom‐economical approach for the incorporation of sulfur into organic frameworks. In recent years, we have witnessed the development of a range of transition‐metal‐based catalytic systems for the control of the regio‐ and stereoselectivity. In this Minireview we highlight the mechanistic background behind this transformation so as to help the design of more specific and active organometallic hydrothiolation catalysts.