Thermal barrier coatings (TBCs) are advanced ceramic layers applied to metal components to provide insulation and protection against high temperatures in extreme operating environments. This study investigated the effects of graphene nanoplatelet (GNP) reinforcement on samarium niobate (SN: SmNbO4) TBCs for extreme environments. Four ceramic top coat compositions were plasma-sprayed onto Inconel 718 substrates: Yttria-stabilized zirconia (YSZ), SmNbO4 (SN), and SN reinforced with 1 and 1.5 wt% GNPs (SN-1GNP, SN-1.5GNP). The research examined microstructural characteristics, phase evolution, mechanical properties and toughening mechanisms. GNP reinforcement significantly improved coating density, with SN-1.5GNP reaching 97.4 ± 1.64% compared to 91.3 ± 1.69% for SN and 86.6 ± 1.47% for YSZ. Hardness and elastic modulus were enhanced by 86.38% and 57.91% for SN-1GNP, and 101.09% and 65.23% for SN-1.5GNP respectively. Moreover, fracture toughness experienced a significant increase from 1.86 ± 0.4 to 5.48 ± 0.7 MPa·m1/2, facilitated by toughening mechanisms, like splat bridging, GNP pull-out, crack arrest and ferroelastic domain switching. Additionally, the SN-1.5GNP coating exhibited a higher adhesion strength of 36.84 MPa, thereby leading to improved layer distribution and lesser chance of delamination. Compared to YSZ, these findings suggest that GNP-reinforced SN coatings offer enhanced performance for extreme environment applications.