Design and fabrication of low-cost, high efficient and robust three-dimensional (3D) microspherical materials for energy conversion and storage is of paramount importance. Here, we first reported a template-free and efficient hydrothermal method to synthesize quaternary AgPb10SbTe12 (AgPbmSbTem+2, m = 10) microspheres comprised of tiny nanoparticles driven by co-doping synergetic dipole-driven aggregation. Due to the effect of site blocking, Ag and Sb atoms tend to segregate into Ag-rich and Sb-rich regions, creating substantial inhomogeneity on the nanoscale. Theoretical calculations confirm the dipole-field-driven mechanism forming the microsphere structure. The inhomogeneous local structure has a high impact on the physical properties of the synthesized compounds: the local Ag/Sb ordering and multiple nanoscale interfaces result in the improved thermoelectric performance and cycling stability during the lithiation/delithiation process in Li ion battery compared to their binary or ternary compounds. (C) 2016 Elsevier B.V. All rights reserved.