Among the intermediate temperature (500–900 K) thermoelectric materials, both the p- and n-type lead telluride (PbTe) compounds have attracted extensive interests. Till date various approaches were adopted to enhance the thermoelectric performance of n-type PbTe-based materials as they show greater potential space for further improvement compared to p-type ones. Herein, a pseudo-ternary n-type (PbTe)0.95-x(Sb2Se3)x(PbS)0.05 system was designed and a large value of ZT = 1.61 at 850 K in case of x = 0.01 was achieved. Two factors are responsible for the improved thermoelectric performance. The incorporation of lead sulfide is the key factor to maintain a high level of power factor above 700 K and the multi-scale hierarchical architectures yield ultra-low thermal conductivity.