Molecular dynamics simulations have been performed to study the diffusion characteristics of di-self interstitial atom (di-SIA) in BCC Fe–Cr alloys and corresponding mass transport of Fe and Cratoms in the temperature range 600–1000 K in the alloys with Cr content 5–25 at%, which is relevant for ferritic/martensitic steels. An original treatment is proposed in this work to account for a mixed migration mode composed of the diffusion of the cluster itself and break-up into a pair of independent SIAs. The ratio of self-diffusion coefficients of Cr and Fe is found to exceed unity in Fe–5Cr and Fe–10Cr alloys, which implies that under cascade-producing damage, 3D-migrating small SIA clusters will effectively contribute to the segregation of Cr to neutral and SIA-preferential sinks, eventually causing radiation induced segregation.