Lanthanum cerate (LC: La2Ce2O7) is a potential material for thermal barrier coating, whose improved toughness is a crucial necessity for the pathway of its industrialization. Herein, we demonstrated a promising approach to develop graphene/carbon nanotube hybrid composite coating using a large throughput and atmospheric plasma spraying method. Graphene nanoplatelets (GNP: 1 wt. %) and carbon nanotube (CNT: 0.5 wt. %) reinforced lanthanum cerate (LCGC) hybrid composite coatings were deposited on the Inconel substrate. The addition of 1 wt. % GNP and 0.5 wt. % CNT in the LC matrix has significantly increased its relative density, hardness, and elastic modulus up to 97.2%, 2–3 folds, and 3–4 folds, respectively. An impressive improvement of indentation toughness (8.04 ± 0.2 MPa m0.5) was observed on LCGC coating, which is ∼8 times higher comparing the LC coating. The toughening was attributed to the factors: such as the distribution of GNPs and CNTs in the LC matrix, synergistic toughening offered by the GNPs and CNTs; (i) GNP/CNT pull-out, (ii) crack bridging and arresting, (iii) splat sandwiching, mechanical interlocking, etc. Finally, this improved toughness offered an exceptional thermal shock performance up to 1721 cycles at 1800 °C, without any major failure on the coating. Therefore, the GNP and CNT-reinforced LC hybrid composite coating can be recommended to open a path for turbine industries.