Metal/single‐crystal‐silicide interface evolution has been examined for Ti/MoSi2 (001) using high‐resolution synchrotron radiation and x‐ray photoemission. Reaction between Ti and Si was observed for temperatures 300≤T≤873 K. At 300 K, it was limited to Ti interaction with the single Si layer terminating the cleaved MoSi2 (001) surface. Analysis of the Si 2pcore level line shape showed two different interfacial reaction products with bonding characteristics of TiSi and a disordered solution of Si in Ti. Interfacial development was dominated by Si outdiffusion at higher temperatures with Si enrichment of the overlayer but not conversion to a silicide.