The efficiency of thermoelectric generators is defined by the thermoelectric performance of materials, as expressed by the thermoelectric figure-of-merit, and their contacts with electrodes. Lead chalcogenide thermoelectric materials and, in particular, PbTe perform well in the 500−900 K temperature range. Here, we have successfully bonded bulk PbTe to Ni electrode to generate a diffusion barrier, avoiding continuous reaction of the thermoelectric legs and conducting electrodes at the operating temperature. We have modified the commonly used spark plasma sintering assembly method to join the Ni electrode to bulk PbTe by driving the total supplied electrical current through the Ni and PbTe solid interfaces. This permits the formation of a thin diffusion layer, roughly 4.5 μm in thickness, which is solely comprised of nickel telluride. This new technique toward the bonding of PbTe with the electrode is beneficial for thermoelectric materials, since high temperatures have proven to be damaging to the quality of bulk material. The interphase microstructure, chemical composition, and crystallographic information were evaluated by a scanning electron microscope equipped with electron backscattered diffraction analysis. The obtained phase at the Ni/PbTe contact is found to be β2 Ni3±xTe2 with a basic tetragonal crystallographic structure of the defective Cu2Sb type.