Catalysts that promote chain walking were discovered in the 1980-1990s. Nickel(II) and palladium(II) complexes of α-diimine ligands were known to efficiently catalyze polymerization of alkenes.  They are also referred as Brookhart's catalysts after being used for making of high molar mass polyolefins for the first time at University of North Carolina at Chapel Hill in 1995. Currently nickel and palladium complexes bearing α-diimine ligands, such as the two examples shown, are the most thoroughly described chain walking catalysts in scientific literature. Ligand design influences not only CW extent but also regio- and stereoselectivity and also the sensitivity of the catalyst to undergo chain-breaking reactions, mainly β-H elimination, influencing achievable molar mass and also the possibility to achieve living polymerization behaviour. Thus stereo block copolymers could be made by combination of living and stereospecific CW polymerization catalysts. Continuous research effort led to design of other ligands which provide CW polymerization catalysts upon complexation to late transition metals. Examples are  β-diimine, α-keto-β-diimine, amine-imine and most recently diamine ligands. As the vast majority of CW polymerization catalysts is based on late-transition metal complexes, having generally lower oxophilicity, these complexes were demonstrated also to provide copolymerisation of olefins with polar monomers like acrylates, alkylvinylketones, ω-alken-1-ols, ω-alken-1-carboxylic acids etc., which was the main initial intention of development of this class of catalysts. These random copolymers could further be utilized in the construction of sophisticated amphiphilic grafted copolymers with hydrophobic polyolefin core and shell based on hydrophilic arms, in some cases made of stimuli-responsive polymers.