Mullite, an extremely useful ceramic material, is doped with transition metal ions. The changes in the electronic properties of these doped materials have been studied by positron annihilation lifetime spectroscopy as well as Doppler broadened line shape analysis. The results on the positron annihilation parameters are characteristic of ionic size, oxidation state and the "d"-electron configuration of the respective transition metals doped in the parent lattice of the mullite. These results, along with the resistivity measurements are suggestive of transition of the parent mullite from an insulator to a semimetal in the modified structure.