CeO2-based redox nanomaterials are widely used in automotive catalysts, solid oxide fuel cell systems and many other applications as highly efficient redox systems. However, these properties suffer thermal deactivation under real operating conditions and accordingly thermal stability is a highly desirable property. We report that highly dispersed and intimately intermixed CeO2-ZrO2-BaO-Al2O3 nanocomposites can be synthesized by direct one-pot synthesis. With an appropriate choice of dopant concentration, a self-assembly mechanism is triggered on calcination at high temperatures to form a network of inter-grown stabilized transition aluminas and CexZr1-xO2 nanocrystals anchored over barium hexaaluminate which show remarkable catalytic properties and an excellent stability against thermal and redox ageing