Cp2TiMe2 has been found to be a competent catalyst for the intramolecular hydroamination/ cyclization of aminoalkynes. In the presence of 5.0 mol% Cp2TiMe2, the hydroamination reactions proceed smoothly at 100–110° C to give five-and six-membered cyclic imines within 4–6 h. After subsequent reduction performed with zinc-modified NaBH3CN at room temperature cyclic amines can be isolated in good yields.