The equilibrium geometry and energy of formation of the polymer molecules (TeO₂)_n with n=2–6 were studied within the ab initio B3LYP method. For each n greater than 2, several stable conformers were found. They are classified into four homologue series: the cyclic molecules built up of corner-sharing TeO₃ pyramids, chain molecules built up of edge-sharing TeO₄ units, cyclic molecules built up of edge-sharing TeO₄ units, and three-dimensional framework structures built up predominantly of corner-sharing TeO₄ units. The latter structures were shown to possess the lowest energy of formation whose limit at n→∞ was found to agree well with the experimental value of the cohesive energy in paratellurite. These molecules could be representative of the local structures in TeO₂ glass.