Pd[κ2‐BiPhePhos][η3‐C3H5][OTf] is reported as an efficient catalyst in the Tsuji–Trost reaction of non‐derivatized allylic alcohols. Both inter‐ and intramolecular stereospecific allylic substitutions with various types of nucleophiles (C‐, S‐, N‐, and O‐centered) were successfully transformed. The desired products were obtained in high yield and high enantiospecificity and the only by‐product was water. The catalyst complexes were also studied and a pivotal effect of a counter ion was found where the chloride promotes decoordination of one of the phosphites that gets oxidized and this leads to decomposition of the catalyst. Application of this robust catalytic system in the total syntheses of bioactive natural products (S)‐cuspareine and (+)‐lentiginosine is demonstrated. More information can be found in the Full Paper by A. Orthaber, J. S. M. Samec et al. (DOI: 10.1002/chem.201705164).