Na8Al6Si6O24(Cl,S)2 materials were prepared with a solid state reaction. The products were studied using X-ray powder diffraction, reflectance measurements as well as X-ray fluorescence, conventional and persistent luminescence, nuclear magnetic resonance, and electron paramagnetic resonance spectroscopies. All materials containing sulfur showed purple tenebrescence, which persisted 2 days in a lit room at room temperature. Considerable blue persistent luminescence peaking at 460 nm and lasting for 1 h was obtained, as well. Persistent luminescence was obtained with irradiation at 365 nm, while tenebrescence required 254 nm. The materials show great promise as low-cost multifunctional optical markers.