Ceramides are waxy lipids that can be found naturally in the outer layer of the skin (called stratum corneum - SC). And they are there in big amounts! The goopy stuff between our skin cells is called extracellular matrix that consists mainly of lipids. And ceramides are about 50% of those lipids (the other important ones are cholesterol with 25% and fatty acids with 15%).
Research shows clearly that they play a super important role in keeping the skin barrier healthy and the skin hydrated. If ceramides in the skin are decreased, more water can evaporate from the skin and there is less water remaining in the skin. So ceramides form kind of a "water-proof" protecting layer and make sure that our skin remains nice and hydrated.
Now the question is only this: If we put ceramides all over our face do they work as well as ceramides already naturally in our skin? Well, the answer is probably a no, but they do work to some extent. The BeautyBrains blog made a fantastic article about ceramides and they have listed a couple of examples about studies showing that ceramides - especially when used in certain ratios with cholesterol and fatty acids - do hydrate the skin and can help to repair the skin barrier.