Over the past decade, nanostructuring has become the core of thermoelectric (TE) material research because it creates numerous internal interfaces that provide an effective way to tune the electrical and/or thermal properties of TE materials. Herein, we report a synthesis of interface-engineered BiSbTe nanostructured TE materials by introducing chemically synthesized molecular Ten2− polyanions into BiSbTe particles, from which BiSbTe nanostructured materials with high-density Te interfacial layers are prepared in thin films and sintered pellets. These Te layers form the contact potential well at the BiSbTe-Te junction to realize energy dependent carrier scattering and scatter phonons effectively, thus resulting in simultaneous improvement in the electrical and thermal properties to increase the ZT value well above 1.3 ± 0.14 that is increased by 40% compared to bulk BiSbTe. The findings of current study can open up new chemical design spaces for interface-engineered electronic and TE materials.