Molecular dynamics (MD) simulation of lithium metasilicate (Li2SiO3) has been performed to study the structural and dynamical characteristics near the glass transition temperature.The geometrical structure analysis reveals that the most probable numbers of ‘‘contact pairs (N)’’ of oxygen atoms satisfy a relation N=3V–6 (V=3 to 7) in a glassy state, where V is the co‐ordination number of oxygen around the lithium. On the other hand, in a liquid state, the most probable structure is represented by N<3V–6, which means an excess ‘free space’ to be available among oxygen atoms. These geometrical changes cause dynamical significance near the transition point.