This work explores how to form and tailor the alloy composition of Fe/FexNi1-x core/alloy nanoparticles by annealing a pre-formed particle at elevated temperatures between 180 – 325 oC. This annealing allowed for a systematic FeNi alloying at a nanoparticle whose compositions and structure began as a alpha-Fe rich core, and a thin gamma-Ni rich shell, into mixed phases resembling gamma-FeNi3 and gamma-Fe3Ni2. This was possible in part by controlling surface diffusion via annealing temperature, and the enhanced diffusion at the many grain boundaries of the nanoparticle. Lattice expansion and phase change was characterized by powder X-ray diffraction (XRD), and composition was monitored by X-ray photoelectron spectroscopy (XPS). Of interest is that no phase precipitation was observed (i.e., heterostructure formation) in this system and the XRD results suggest that alloying composition or alloy gradient is uniform. This uniform alloying was considered using calculations of bulk diffusion and grain boundary diffusion for Fe and Ni self-diffusion, as well as Fe-Ni impurity diffusion is provided. In addition, alloying was further considered by calculations for Fe-Ni mixing enthalpy (Hmix) and phase segregation enthalpy (HSeg) using the Miedema model, which allowed for the consideration of alloying favorability or core-shell segregation in the alloying, respectively. Of particular interest is the formation of stable metal carbides compositions, which suggest that the typically inert organic self-assembled monolayer encapsulation can also be internalized.