Interaction of the tetradentate redox-active 6,6′-[1,2-phenylenebis(azanediyl)]bis(2,4-di-tert-butylphenol) (H4L) with TeCl4 leads to neutral diamagnetic compound TeL (1) in high yield. The molecule of 1 has a nearly planar TeN2O2 fragment, which suggests the formulation of 1 as TeIIL2−, in agreement with the results of DFT calculations and QTAIM and NBO analyses. Reduction of 1 with one equivalent of [CoCp2] leads to quantitative formation of the paramagnetic salt [CoCp2]+.−, which was characterised by single-crystal XRD. The solution EPR spectrum of [CoCp2]+.− at room temperature features a quintet due to splitting on two equivalent 14N nuclei. Below 150 K it turns into a broad singlet line with two weak satellites due to the splitting on the 125Te nucleus. Two-component relativistic DFT calculations perfectly reproduce the a(14N) HFI constants and A∥(125Te) value responsible for the low-temperature satellite splitting. Calculations predict that the additional electron in 1.− is localised mainly on L, while the spin density is delocalised over the whole molecule with significant localisation on the Te atom (≥30 %). All these data suggest that 1.− can be regarded as the first example of a structurally characterised monomeric tellurium–nitrogen radical anion.