Positron annihilation angular correlation measurements have been performed for the neutron irradiated various metals and ceramics in order to obtain the information of the microvoids and positronium formation in them. Positronium (Ps) formation was observed in Nb containing a small amount of oxygen and Fe-15%Cr-16%Ni-0.006%B^. In practical steels such as JPCA and JFMS no Ps formation was observed. High temperature deformation might induce microvoids into metals, but the positron annihilation angular correlation measurements could not confirm this. In non-metallic materials neutron irradiated no Ps formation has so far been observed