The structure and composition of higher manganese silicide (HMS) films on Si(111) substrate are studied by high-resolution transmission electron microscopy, electron diffraction, and energy-dispersive X-ray spectroscopy. The formation of Mn4Si7 HMS film by the deposition of the gas-phase manganese onto silicon at 1040°C is observed. The film/substrate interface is semicoherent and does not contain any intermediate layer. The interface structure is refined by computer simulation. The orientation relationship \(\left( {\overline 1 \overline 2 4} \right)\left[ {443} \right]M{n_4}S{i_7}||\left( {1\overline 1 \overline 1 } \right)\left[ {001} \right]Si\) between the film and substrate is determined.