We present a novel freeze-drying combustion method for synthesis of macroporous powders with nano-network, using Sm0.2Ce0.8O1.9 (SDC) as an example. The metal nitrate salt solution mixed with glycine is frozen to form homogeneous nitrate/glycine mixture and then freeze-dried through sublimation of ice crystals. Upon combustion of the freeze-dried mixture, SDC powders with macroporous microstructure consisting of 10-20 nm nanocrystals, high surface area and excellent sinterability are achieved. High resolution transmission electron microscopy (HRTEM) analysis indicates that nanodomains due to aggregation/segregation of dopants in the SDC powders obtained from freeze-drying combustion are much smaller than those in the SDC powders synthesized by the conventional nitrate solution combustion approach, demonstrating better elemental homogeneity and improved conductivity. Using low cost precursors and simple processing conditions, freeze-drying combustion can be a versatile method to synthesize nanocrystalline powders with excellent composition homogeneity for broad applications. (C) 2016 Elsevier Ltd. All rights reserved.