The main physicochemical phenomena occurring at the interface of Bi₂Te₃—Sb₂Te₃ and Bi₂Te₃—Bi₂Se₃ crystals with Bi-, Sb-, Sn-, Pb-, Cd-, Ag- and Ni-based metallic alloys (contact materials) are analyzed. It is shown that crystal surface damage, diffusion of the contact material into the near-contact region accompanied by changes in carrier concentration and work function, and the formation of intermediate-phase layers at the interface play a decisive role in the formation of electrical and adhesive properties of the contacts. It is demonstrated that low-resistance transition contacts with stable electrical parameters and sufficient adhesion strength can be fabricated.