The phase diagram of the Sb2Te3+Bi2Te3+Se+Te)1-x(Sm)х system is studied using differential thermal analysis, X-ray diffraction, microstructural analysis, microhardness and density measurements. The influence of Sm element on the property of solid solution (Sb2Te3+Bi2Te3+ Se+Te) of p-type has been studied. At room temperatures, the (Sb2Te3+Bi2Te3+Se+Te) based solid solution extends to 5 at.% Sm.