Selective hydrogenations lay at the heart of many industrial processes. The archetypal catalysts for this class of reactions are generally prepared by ‘metal poisoning’ strategies: the active metal is protected and selectively deactivated with vari- ous compounds. This approach has been applied for decades, with limited understanding. Low product selectivity and pres- ence of toxic elements in the catalyst pose severe constraints in the utilization of these materials in the future. Thus, to de- velop more sustainable catalysts, this field has recently gained momentum. This Review analyzes the concepts and frontiers that have been developed in the last decade: from nanostruc- turing less conventional metals in order to improve their ability to activate H2, to the use of oxides as active phases, from alloy- ing, to the ensemble control in hybrid materials, and site isola- tion approaches in single-site heterogeneous catalysts. Particu- lar attention is given to the hydrogenation of alkynes and ni- troarenes, two reactions at the core of the chemical industry, importantly applied in the manufacture of polymers, pharma- ceuticals, nutraceuticals, and agrochemicals. The strategies here identified can be transposed to other relevant hydrogena- tions and can guide in the design of more advanced materials.