Tracer diffusion coefficients are calculated in different phases in the Mo–Si system from diffusion couple experiments using the data available on thermodynamic parameters. Following, possible atomic diffusion mechanism of the species is discussed based on the crystal structure. Unusual diffusion behaviour is found in the Mo 5 Si 3 and Mo 3 Si phases, which indicate the nature of defects present on different sublattices. Further the growth mechanism of the phases is discussed and morphological evolution during interdiffusion is explained.