In a recent letter to Nature Materials, we reported how anhydrous powders of sugars and surfactants suspended in oil can spontaneously form molten glasses with nanometer size domains of sugar and liquid oil without mixing. In this presentation, we will discuss the latest findings on the liquid-crystalline phase behavior and microstructure of glucamide- and lactobionamide-based surfactants in sucrose/trehalose glasses. We will also discuss the latest findings on self-assembly in gallium metal. Due to the large refractive index difference of gallium with organic materials, it is an ideal candidate for varied optoelectronics applications. Tuning of self-assembly in gallium by temperature variation would lead to tunable photonic properties.