Electrodeposition of solid solution films PbSe1-xTex(0 less than or equal to x less than or equal to 1) from acid aqueous electrolytes by simultaneous cathodic reduction of Pb-II, Se-IV and Te-IV compounds, has been investigated. It has been established that electrosynthesis of PbSe1-xTex proceeds at potentials more positive than the Nernst potential EPb2+/Pb0 due to chemical interaction between underpotentially deposited Ph adatoms and overpotentially deposited selenium and tellurium, formed by the reduction of Se-IV and Te-IV anion forms. Dependence of solid solution composition on both electrolyte composition and applied electrode potential has been presented. Periodic change of cathodic polarization level of the electrode was used to produce the multilayer periodic structures PbSe/PbSe1-xTex with periods 2.5-10 nm.