The purpose of the present study is to investigate the influence of fuel additives [2-methoxyethyl acetate (MEA)] plus thermal barrier coating (TBC) on diesel engine performance, combustion, and emission characteristics. A plasma spray coating (PSC) technique was used to coat the cylinder head, valves, and piston crown with ZrO2/Al2O3 of about 150:150 mu m. The additives are in the ratio between 0.5 and 2.0%, with 0.5% intervals. They were added to neat diesel fuel, by volume, respectively. In general, the ceramic coating as a thermal barrier improves the efficiency by reducing energy losses. The experiment was conducted in a single-cylinder water-cooled direct-injection (DI) diesel engine. The engine was run at a constant speed of 1500 rpm and fixed injection pressure of 200 bar. In the first phase, engine components were coated with ZrO2/Al2O3 by using the PSC techniques and thickness of 150 mu m each. In the second phase, experiments were carried out in the thermal-barrier-coated engine by using various blends of fuel additives (MEA). The experiments were conducted at various loads, such as 25, 50, and 75% and maximum load, and the results were compared. The effect of TBC decreased the NOx emission, and the performance profile was found improved. The experimental results show that the combined effect of TBC and fuel additive changes the performance and simultaneously reduces the NOx emission. NOx emission was reduced by 40% in the thermal-barrier-coated engine, and it was further reduced by 10% in the fuel additive plus thermal-barrier-coated engine.