The fifth chapter of the book updates enantioselective nickel-catalysed hydrovinylation, hydrophosphination, hydrocyanation, and hydroalkynylation reactions since 2004. In particular, the last decade has known many important advances in the field of asymmetric nickel-catalysed hydrovinylations of alkenes, probably related to the fact that nickel complexes have been significant catalysts in hydrovinylation reactions. All these novel procedures have used very low catalyst loadings of highly versatile phosphoramidite ligands derived from Feringa's ligand, with NaBArF as catalyst activator, providing excellent enantioselectivities in all cases. In the area of nickel-catalysed asymmetric hydrophosphination of alkenes, the first highly enantioselective reaction has been reported along with the first nickel-catalysed hydroalkynylation of 1-arylbuta-1,3-dienes. Moreover, very good results have been reported for nickel-catalysed hydrocyanation of arylalkenes. All the formed chiral products from hydrovinylation, hydrophosphination, hydrocyanation, and hydroalkynylation reactions of alkenes constitute useful building blocks in asymmetric organic synthesis since they can be readily transformed into a variety of other common functional groups.