Aqueous solutions of Me2Te(OH)2 and (CH2)4Te(OH)2 readily absorb carbon dioxide giving rise to the formation of the dialkyltelluroxane carbonates (Me2TeOTeMe2CO3)n (1) and HO(CH2)4TeOTe(CH2)4CO3Te(CH2)4OH·2H2O (2·2H2O), which were characterised by 13C MAS and 125Te MAS NMR spectroscopy as well as X‐ray crystallography. The spatial arrangement of the tellurium atoms is defined by C2O2 donor sets in the primary coordination sphere and one or two secondary Te···O contacts, which involve coordination of the carbonate moieties. In turn, the different Te–O coordination modes render a lack of symmetry to the carbonate moieties, which show significantly different C–O bond lengths, an important feature when contemplating the C–O bond activation in carbonates. The structural and spectroscopic parameters of 1 and 2 are discussed in comparison with other heavy p‐block element carbonates. In solution, electrolytic dissociation of 1 and 2 takes place.