Nanomaterials are vital in catalysis, sensing, energy storage, and biomedicine and now incorporate multiprincipal element materials to meet evolving technological demands. However, achieving a uniform distribution of multiple elements in these nanomaterials poses significant challenges. In this study, various Cu-Ni compositions were used as a model system to investigate the formation of bimetallic nanoparticles by employing computer simulation molecular dynamics methods and comparing the results with observations from solution-combustion-synthesized materials of the same compositions. The findings reveal the successful synthesis of 12-18 nm bimetallic Cu-Ni nanoparticles with high phase homogeneity, alongside phase-segregated nanoparticles predicted by molecular dynamics simulations. Based on the comparison of the experimental and computational data, a possible scenario for phase segregation during the synthesis was proposed. It includes clustering of the atoms of the same type in an initial solution or the stage of gel formation and further developing segregation during the combustion/cooling stage. The research concludes that early synthesis stages, including particle preformation, significantly influence the phase homogeneity of multiprincipal element alloys. This study contributes to understanding nanomaterial formation, offering insights for improved alloy synthesis and enhanced functionalities in advanced applications.