A new technique using radioactive 31Si (half‐life =2.62 h), formed in a nuclear reactor, as a marker for studying silicide formation is described. A few hundred angstroms of radioactive silicon is first deposited onto the silicon substrate, followed immediately by the deposition of a few thousand angstroms of the metal. When the sample is heated, a silicide is first formed with the radioactive silicon. Upon further silicide formation, this band of radioactive silicide can move to the surface of the sample if silicide formation takes place by diffusion of the metal or by silicon substitutional and/or vacancy diffusion. However, if the band of radioactive silicide stays at the silicon substrate interface it can be concluded that silicon diffuses by interstitial and/or grain‐boundary diffusion. This technique was tested by studying the formation of Ni2Si on 〈100〉 silicon at 330 °C. From a combination of ion‐beam sputtering, radioactivity measurement, and Rutherford backscattering it is found that the band of radioactive silicide moves to the surface of the sample during silicide formation. From these results, implanted noble‐gas marker studies and the rate dependence of Ni2Si growth on grain size, it is concluded that nickel is the dominant diffusing species during Ni2Si formation, and that it moves by grain‐boundary diffusion.