The controlled synthesis of large-scale nanocrystalline metals and alloys with predefined architecture is in general a big challenge, and making full use of these materials in applications still requires greatly effort. The combustion synthesis technique has been successfully extended to prepare large-scale nanocrystalline metals and alloys, especially iron alloy, such as FeC, FeNi, FeCu, FeSi, FeB, FeAl, FeSiAl, FeSiB, and the microstructure can be designed. In this issue, recent progress on the synthesis of nanocrystalline metals and alloys prepared by combustion synthesis technique are reviewed. Then, the mechanical and tribological properties of these materials with microstructure control are discussed.