A concentration series of Y3Al5O12:Ce solid solutions were prepared, and the composition demonstrating the highest X-ray luminescence intensity of cerium was identified. Based on the best composition, a series of luminescent diamond–Y3Al5O12:Ce composite films were synthesized using microwave plasma-assisted chemical vapor deposition (CVD) in methane–hydrogen gas mixtures. Variations in the amounts of the embedded Y3Al5O12:Ce powders allowed for the fine-tuning of the luminescence intensity of the composite films.