Thermoelectric materials are considered promising candidates for thermal energy conversion. This study presents the fabrication of Zn– and Ce–alloyed In2O3 with a porous structure. The electrical conductivity was improved by the alloying effect and an ultra–low thermal conductivity was observed owing to the porous structure, which concomitantly provide a distinct enhancement of ZT. However, SiO2 nanoparticle additives react with the matrix to form a third-phase impurity, which weakens the electrical conductivity and increases the thermal conductivity. A thermoelectric module was constructed for the purpose of thermal heat energy conversion. Our experimental results proved that both an enhancement in electrical conductivity and a suppression in thermal conductivity could be achieved through nano–engineering. This approach presents a feasible route to synthesize porous thermoelectric oxides, and provides insight into the effect of additives; moreover, this approach is a cost-effective method for the fabrication of thermoelectric oxides without traditional hot-pressing and spark–plasma–sintering processes.