Bimetallic CuNi nanoparticles of various nominal compositions (1:3, 1:1, 3:1) supported on ZrO2 were employed for operando spectroscopy and theoretical studies of stable surface compositions under reaction conditions of catalytic methane decomposition up to 500 degrees C. The addition of Cu was intended to increase the coke resistance of the catalyst. After synthesis and (in situ) reduction the CuNi nanoparticles were characterized by HR-TEM/EDX, XRD, FTIR (using CO as probe molecule) and NAP-XPS, all indicating a Cu rich surface, even when the overall nanoparticle composition was rich in Ni. Density functional (DF) theory modelling, applying a recently developed computational protocol based on the construction of topological energy expressions, confirmed that in any studied composition Cu segregation on surface positions is an energetically favourable process, with Cu preferentially occupying corner and edge sites. Ni is present on terraces only when not enough Cu atoms are available to occupy all surface sites. When the catalysts were applied for methane decomposition they were inactive at low temperature but became active above 425 degrees C. Synchrotron -based operando NAP-XPS indicated segregation of Ni on the nanoparticle surface when reactivity set in for CuNi-ZrO2. Under these conditions C is core level spectra revealed the presence of various carbonaceous species at the surface. DF calculations indicated that both the increase in temperature and especially the adsorption of Clix groups (x = 0-3) induce the segregation of Ni atoms on the surface, with CH3 providing the lowest and C the highest driving force. Combined operando and theoretical studies clearly indicate that, independent of the initial surface composition after synthesis and reduction, the CuNi-ZrO2 catalyst adopts a specific Ni rich surface under reaction conditions. Based on these findings we provide an explanation why Cu rich bimetallic systems show improved coke resistance. (C) 2016 The Authors. Published by Elsevier B.V.