The synthesis and structural characterization of new layered rare-earth silicates K-3[M1-aCeaSi3O8(OH)(2)], M = Y3+, Tb3+, a << 1 (AV-22 materials), have been reported. These materials combine the properties of layered silicates, such as intercalation chemistry, and photoluminescence and may find applications in new types of sensor devices. For mixed Tb/Ce-AV-22, evidence has been found for the energy transfer from the large Ce3+ 4f(1) -> 5d(1) broad band to the sharp Tb3+ 4f(8) lines. This energy transfer allows the fine-tuning of the color emission in the blue-green region of the chromaticity diagram. Upon Ce3+ excitation (342 nm), the radiance of Tb/Ce-AV-22 is approximately 2 times higher than that measured under direct Tb3+ excitation, which reinforces the existence of effective room-temperature Ce3+-to-Tb3+ energy transfer.