Heterostructured nanoparticles (NPs) offer great opportunities for applications in areas such as biomedicine, renewable energy, information processing, and data storage by virtue of their embedded multiple functionalities and enhanced magnetic, [1,2] optical, [3] and catalytic performance [4] arising from the interactions of the individual components within the NPs.To understand the fundamental nature of these interactions, as well as to utilize them more efficiently, it is imperative to develop synthesis methods to prepare heterostructured NPs with high-quality interfaces and surfaces. Several heterostructures have been synthesized by the seed-growth approach using wet chemical methods, [5][6][7][8][9] sometimes followed by a chemical vapor deposition (CVD) process. [10,11] However, solution-based approaches make it difficult to obtain contamination-free interfaces and surfaces. Moreover, the integration of solution-synthesized NPs into vacuum-based micro-and nanoelectronics fabrication processes has been remarkably challenging. On the other hand, gas-phase techniques have the intrinsic merit of producing a clean interface and surface, yet only a few attempts have been made to produce heterostructured NPs [12][13][14] other than the widely reported core/shell NPs consisting of metal cores surrounded by an oxide shell of the same metal.[1] Here, we demonstrate that binary metallic (Au-Co and Ag-Fe) NPs with distinctively different heterostructures at the single-particle level can be prepared directly in the gas phase via phase separation and surface segregation. This synthesis approach is ultra high vacuum (UHV) compatible, and yields high quality interfaces and surfaces; the synthesized NPs can also be made water soluble [15] and functionalized for further chemical processing. This approach can also be extended to various other material systems such as alloys and semiconductors. [13] In this work, we have selected a combination of ferromagnetic elements (Co or Fe) and noble metals (Au or Ag) as the model system. Several characteristic properties make this system a good starting point for the synthesis of heterostructured NPs. For instance, at room temperature Co and Au do not alloy and readily phase separate in the bulk form or clusters of more than several hundred atoms. [16,17] The ferromagnetic elements have a smaller atomic size than the noble metals. Consequently, the mismatch in atomic size causes the strain energy to increase when the atoms are mixed as compared to the lower energy segregated state.[18] The ferromagnetic elements generally have a higher surface energy than the noble metals (Co (111) 3.23 J m -2 , Au (111) 1.61 J m -2 ), [19] which makes it more preferable for the noble metals to be present at the surface and leads the system towards surface segregation. Numerical simulations of binary metal NPs also suggest that noble metals are energetically favored to be present at the surface as compared to transition metals. [18,20] Though the combination of phase separation and large differences in s...