We report small-angle neutron scattering studies on the microstructure network in bulk (Bi,Sb)2Te3 synthesized by the melt-spinning (MS) and the spark-plasma-sintering (SPS) process. We find that rough interfaces of multiscale microstructures generated by the MS are responsible for the large reduction of both lattice thermal conductivity and electrical conductivity. Our study also finds that subsequent SPS forms a microstructure network of ∼10 nm thick lamellae and smooth interfaces between them. This nanoscale microstructure network with smooth interfaces increases electrical conductivity while keeping a low thermal conductivity, making it an ideal microstructure for high thermoelectric efficiency.