A slow positron beam was used to investigate the solid state reaction of Co/Si and Co/Ti/Si. Variable-energy (0-20 keV) positrons were implanted into samples at different depths. The Doppler broadening of the annihilation -y-ray energy spectra, measured at a number of different incident positron energies were characterized a line-shape parameter “5”. It was found that the measured S parameters were sensitive to thin film reaction and crystalline characteristics. In particular, the S parameter of epitaxial CoSi2 formed by the ternary reaction was quit different from that of the polycrystalline CoSi2 formed by direct reaction of Co with Si.