Mild and facile preparations of 2-substituted or 2,3-disubstituted indole compounds were achieved by RhH(CO)(Ph(3)P)(3) (4-10 mol %)-catalyzed reaction of N-propargylanilines in hexafluoroisopropyl alcohol (HFIP). The formation of indoles was proven to be derived from an o-allenylaniline intermediate, which was generated by the Rh(I)-catalyzed amino-Claisen rearrangement of N-propargylanilines. The catalytic system is also available for the one-pot synthesis of indoles by reacting N-alkylaniline (1 equiv) with propargyl bromide (1.3 equiv) in the presence of K(2)CO(3) (3 equiv) in HFIP. The active catalyst was proven to be [Rh(CO)(Ph(3)P)(2)]OCH(CF(3))(2) generated in situ from RhH(CO)(Ph(3)P)(3) and HFIP. The structure of [Rh(CO)(Ph(3)P)(2)]OCH(CF(3))(2) was confirmed by single-crystal X-ray crystallographic analysis.