Titanium bis(diethylamido) complex 1, which contains a carbon-bridged bis(indolyl) ligand, was obtained in 69% yield from the reaction of Ti(NEt2)4 with the corresponding bis(indole) ligand. Its molecular structure in the crystal was unequivocally determined by a single-crystal X-ray diffraction analysis. Furthermore, we examined applications of 1 as a catalyst for the intermolecular hydroamination of alkynes. When using phenylacetylene or 1-hexyne as alkynes, the Markovnikov products were obtained selectively, while the reaction with 1-phenyl-1-propyne afforded an imine of phenylacetone.