Five-component electroceramics based on solid solution PbTiO 3–PbZrO 3–PbNb 2/3Zn 1/3O 3–PbSb 2/3Mn 1/3O 3–PbNb 2/3Mn 1/3O 3 was studied. The chemical composition of the solid solution varied with PbTiO 3 content. Thus samples exhibiting rhombohedral crystalline structure, tetragonal structure, as well as samples exhibiting compositions from the morphotropic phase boundary region (MBR) were under investigation. Conventional mixed oxide method was used for the powder preparation. Hot pressing technique was employed for fabrication of ceramic pellets. To produce pyroelectric activity the samples underwent high voltage poling (HVP) or low voltage poling (LVP). Thermal stability of the pyroelectric coefficient was measured according to both quasi-static γ ST( T) and dynamic method γ D( T). The customised measuring system was developed. Dependence of the dielectric permittivity ε 33 /ε 0 of poled samples on temperature was also recorded. Results are reported and explanation of the observed temperature traces for γ ST( T), γ D( T), and ε 33 /ε 0( T) is given taking into consideration the two different methods of poling the multi-component samples.