During the last few decades, rhodium-catalysed asymmetric hydrogenation of diverse alkene classes has emerged as a powerful synthetic tool in the pharmaceutical industry, contributing to the manufacturing of chiral drugs, recent drug candidates for clinical trials, and major synthetic precursors of drugs. Numerous efficient chiral rhodium complexes, most of which are derived from enantiopure phosphorus ligands, have been employed for the preparation of chiral drugs and intermediates thereof. This review article is intended to provide an updated overview of the most striking contributions in this field, organised according to substrate class: acrylate derivatives, itaconate derivatives, α-substituted enamides, α-arylenol acetates, and minimally functionalised olefins.