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This study analyzed the fabrication and characterization of polybenzoxazine/polydopamine/ceria as tertiary nanocomposites. To this end, a new benzoxazine monomer (MBZ) was fabricated based on the well-known Mannich reaction of naphthalene-1-amine, 2-tert-butylbenzene-1,4-diol and formaldehyde under ultrasonic-assisted process. Polydopamine (PDA) was used as dispersing polymer nanoparticles and surface modifier for CeO2 by in-situ polymerization of dopamine with the assistance of ultrasonic waves. Then, nanocomposites (NC)s were manufactured by in-situ route under thermal conditions. The FT-IR and 1H-NMR spectra confirmed the preparation of the designed MBZ monomer. The FE-SEM and TEM results showed the morphological aspects of prepared NCs and illustrated the distribution of CeO2 NPs in the polymer matrix. The XRD patterns of NCs showed the presence of crystalline phases of nanoscale CeO2 in an amorphous matrix. The TGA results reveal that the prepared NCs are classified as thermally stable materials.