The structures of interfaces in NiAl-matrix in situ composites reinforced by TiC particulates were studied by means of high-resolution electron microscopy (HREM). No consistent orientation relationship between TiC particles and the NiAl matrix was found. In most cases, TiC particles bonded well to the NiAl matrix free from any interfacial phases. However, in some cases, an interfacial amorphous layer with a thickness of about 3 nm was found. The annealed NiAl–TiC composite showed a good chemical compatibility between the TiC particles and the NiAl matrix, though, some interfacial layers between TiC and NiAl, which were determined to be C-deficient TiC, were found. NiAl precipitates were observed in the TiC particles of the annealed specimens.