Amidomethylation of Te(0) (elemental tellurium) as well as Te(II) (aryltellurium bromide, in situ) proceeds readily under mild conditions. It involves oxidative insertion of low valent tellurium into the C–Br bond of N-substituted α-bromoacetamides and provides a direct synthetic route to the stable, crystalline amidomethyltellurium(IV) dibromides, (RR′NCOCH₂)₂TeBr₂ (RR′N = Et₂N (1b), MePhN (2b), Me(c-Hex)N (3b), O(CH₂CH₂)₂N (4b)) and (Et₂NCOCH₂)ArTeBr₂ (Ar = mesityl, 5b; 1-naphthyl, 6b). Biphasic bisulfite reduction of the dialkyltellurium dibromides afforded yellow to orange coloured amido functionalized symmetrical telluroethers, (RR′NCOCH₂)₂Te (RR′N = Et₂N (1), MePhN (2), Me(c-Hex)N (3), O(CH₂CH₂)₂N (4)), of which compound 2 was isolated as a crystalline solid. Oxidation of the new dialkyltelluroethers with dihalogens (Br₂, I₂) or SO₂Cl₂ afforded the corresponding amidomethyltellurium(IV) dihalides, (RR′NCOCH₂)₂TeX₂ (RR′N = Et₂N, X = Cl (1a), Br (1b), I (1c); RR′N = MePhN, X = Cl (2a), Br (2b), I (2c); RR′N = Me(c-Hex)N, X = Cl (3a), Br (3b), I (3c); RR′N = O(CH₂CH₂)₂N, X = Cl (4a), Br (4b), I (4c)) that were characterized by elemental analyses and multinuclear (¹H, ¹³C, ¹²⁵Te) NMR. Single crystal X-ray data on 1b, 1c, 2, 2b, 2c, 4b, 5b and 6b suggest that the N-substituted amidomethyl group acts as a small-bite chelating ligand, via intramolecular 1,4-Te⋯O coordination, towards the Te(IV) centre. Steric congestion around Te(IV) due to intramolecular secondary bonding interaction(s), reduced electrophilicity of Te(II) and the partial positive charge on N due to the resonating character of the amido group presumably prevents these atoms from participating in the intermolecular associative forces in the solid state. Instead, weak C–H⋯O and C–H⋯X H-bonding interactions take centre-stage in the self assembly.