Transition metals (TMs) and their complexes are current examples of such materials which show new functionality, improved performances and greater versatility and have become the key drivers of innovation. In the same scenario, we present a series of new TM tellurate (TMTeO4 with TM = Co, Ni or 2×TM0.5Te0.5O2 analogous to VO2) compounds, for the first time. To the best of our knowledge, these TMTeO4 systems are completely new to explore, both from the fundamental as well as the applied physics perspectives. Towards this, the analysis of detailed neutron diffraction measurements will explore the structural and magnetic correlations to unravel the underlying phenomenon.