The synthesis and structural characterization of two new homo‐ and heteroleptic tetravalent cerium complexes with tert‐butoxo and heteroarylalkenolate ligands of the general formula [Ce(OtBu)2–xLx+2] [x = 2 (1), x = 0 (2)] [L = Dmox‐CHC(CF3)O] is described. Their thermal decomposition behavior as well as their potential as single‐source precursor for the fabrication of nanostructured ceria was evaluated. By using the heteroleptic alkoxide complex 2 as metal organic precursor, an efficient synthesis of highly crystalline CeO2 QDs with a narrow size distribution was achieved by microwave assisted solvothermal synthesis in NMP. It was found that an expedient choice of precursor enabled the replacement of additives like bases or other mineralizer and opens an efficient pathway for controlled nucleation of metal oxide nanoparticles.