You mean like a ceramic, heat reflective coating, right? That's actually fairly common practice in some race engines. I did it on my supercharged 490" FE. I had the combustion chambers, valves, and intake and exhaust ports coated at this place called Swain coatings in Michigan. Barry at Survival Motorsports got it done for me, because I bought the Blue Thunder heads from him. I also had the pistons coated at Diamond Pistons when they were made for the engine.
The theory is that the less heat escapes into the castings and cooling system, the more heat is available to make pressure in the cylinder, and thus an engine with coatings will deliver more horsepower than one without.
In addition to Swain, there is an outfit in Texas I think, called Polydyn coatings, that also does this work. Blair Patrick uses them, and I've gotten pistons from him before that have this coating on them. I kind of liked it better than the Swain coatings.
Applications of the coatings is critical, and if you don't do it right, they will flake off and become useless. I tried to do it myself once with some products from a place called Techline coatings, but despite my best efforts, a teardown on the engine after the dyno sessions showed that the coatings on the pistons were starting to flake off. On the other hand, I've torn down engines where the pistons have been professionally coated, and everything on the piston tops has looked intact. So if done correctly, there is no doubt that the coatings will live.
Hope that helps - Jay