In this work, we describe the use of novel environmentally friendly industrial processing techniques to produce nano-sized crystallite powders and fabricate bulk ceramic pellets of functional materials. We present the application of a microwave (MW)-assisted synthesis process to fabricate the un-doped and doped ceria phases CeO2−δ, Ce0.8Gd0.1Sm0.1O1.9, Ce0.85Gd0.15O1.925, Ce0.85Sm0.15O1.925 and Ce0.8Sm0.18Ca0.02O1.9 for potential application in solid oxide fuel cells. We find that the composition Ce0.8Sm0.18Ca0.02O1.9 may be most beneficial owing to the highest ionic conductivities encountered in the corresponding sintered ceramics. As a next step, we tested a MW-assisted sintering process to fabricate dense Ce0.8Sm0.18Ca0.02O1.9 pellets. We find that both the synthesis and sintering process can be achieved by using MW heat sources and the entire fabrication process may be regarded a “green ceramic processing”.