The selective hydrogenation of alkynes to alkenes is an important type of organic transformation with large-scale industrial applications. This transformation requires efficient catalysts with precise selectivity control, and palladium-based metallic catalysts are currently employed. Here we show that four-coordinated cationic nickel(II) confined in zeolite can efficiently catalyze the selective hydrogenation of acetylene to ethylene, a key process for trace acetylene removal prior to the polymerization process. Under optimized conditions, 100% acetylene conversion and an ethylene selectivity up to 97% are simultaneously achieved. This catalyst system also exhibits good stability and recyclability for potential applications. Spectroscopy investigations and density functional theory calculations reveal the heterolytic dissociation of hydrogen molecules and the importance of hydride and protons in the selective hydrogenation of acetylene to ethylene. This work provides an efficient strategy toward active and selective zeolite catalysts by utilizing the local electrostatic field within the zeolite confined space for small-molecule activation and by linking heterogeneous and homogeneous catalysis.