For the development of catalytically active and selective Ni nanoparticle (NP) catalysts both the choice of the synthesis method and the selection of stabilizer are key parameters. A series of Ni NPs were synthesized in various ionic liquids (Ni/ILs) and applied as catalysts for the chemoselective reduction of 2‐cyclohexen‐1‐one ( 1 ), as a representative of the group of α,β‐unsaturated carbonyl compounds with industrial relevance. The Ni/ILs systems were found to be efficient catalysts for the selective hydrogenation of 1 to cyclohexanone ( 2 ) under quite mild reaction conditions (130‐170 °C, 10 bar H 2 , 1 /Ni molar ratio of 100/1), achieving high conversions in a short reaction time (1 h). The oxidized counterparts (Ni‐NiO/ILs) showed to be active for the selective catalytic transfer hydrogenation (CTH) of 1 to 2‐cyclohexen‐1‐ol ( 3 ) with 2‐propanol, also under mild reaction conditions (150 °C, 48 h, 1 /Ni ratio of 50/1).