Herein, the effect of P concentration in highly P‐doped epitaxial Si films on the formation of Ti silicide therein are investigated. Ti films sputter‐deposited on P‐doped Si substrates are annealed at different temperatures, and the thus obtained samples are characterized by X‐ray diffraction (XRD) and transmission electron microscopy. The former technique revealed that the formation of C54 is suppressed by high P concentrations, while the resistivity of Ti silicide are shown to be independent of P concentration when the C54 phase is fully formed under the condition of sufficient thermal budget. Most importantly, this work confirms the occurrence of a silicidation delay in in situ P‐doped epitaxial Si films and demonstrates that this delay increases the temperature of the C49 to C54 phase transition of Ti silicide.