Alkaline solution, especially diphosphate solutions, can be used as electrolytes for the galvanic deposition of p-type semiconductors. A ternary Bi–Sb–Te alloy semiconductor was deposited at a Ni-covered cathode surface at potentials lower than −0.6 V (Ag/AgCl), under potentiostatic condition in well-stirred solutions. Additionally, it was possible to deposit antimony telluride, a binary p-semiconductor, from the ternary electrolyte. The kinetics of the process was investigated by cyclic voltammetric measurements. The influence of the electrolyte convection on the electrocrystallization was analysed with the help of rotating disc electrode. The semiconductor layers were characterized by electrochemical impedance spectroscopy.