The interaction between mechanics and chemistry plays an essential and critical role in the surface segregation and relaxation in nanoscale alloys. Following the thermodynamics analysis based on surface eigenstress, the present study takes the free-standing nanometer thick films of Ni1 –x Cux solid solutions with face-centered cubic (fcc) crystalline structures as an example to investigate surface segregation of Cu and relaxation of the films. Hybrid Monte Carlo and Molecular Dynamics (MCMD) simulations are conducted on free-standing Ni1 –x Cux alloys of (100) and (111) nanofilms. The MCMD simulations verify the theoretical analytic results and determine the values of parameters involved in the theoretical analysis. Especially, the parameter of the differentiation in reference chemical potential behaves like the molar free energy of segregation in the McLean adsorption isotherm, and the differentiation in chemical composition induced eigenstrain plays also an important role in surface segregation and relaxation. The integrated theoretical and numerical study exhibits that both surface excess Cu concentration and apparent biaxial Young's modulus of Ni1 –x Cux nanofilms depend on the nominal Cu concentration and the film thickness.