In partial hydrogenation of highly unsaturated compounds, high-performance heterogeneous catalysts usually consist of multi-metallic systems providing enhanced selectivity. These materials often undergo complex segregation phenomena and to understand their function, a surface-sensitive in situ methodology is crucial. Recently, we reported a novel family of ternary Cu–Ni–Fe catalysts for propyne hydrogenation with exceptional selectivity to propene. Herein, we detail our study on the surface composition and electronic state of two representative samples (Cu_2.75Ni_0.25Fe and Cu₃Fe) using in situ X-ray photoelectron (XPS) and X-ray absorption (XAS) spectroscopies. Surface segregation phenomena during activation of the catalyst precursors (calcination and reduction) and hydrogenation reaction were evaluated. The multiple functions of nickel in the catalyst, which account for the extraordinary alkene selectivity, are unravelled.