The methods and materials described herein provide novel and simple procedures for the preparation of nano/macroporous glasses, in which the pore structure is characterized by interconnected pores of, e.g. both hundreds of micrometers and several to tens of nanometers in size. Such materials may be used for enhanced bone regeneration, bioscaffolds, drug delivery devices, and filtration media, among other uses. For example, silica-based bone tissue scaffolds are made with a controlled nano/macroporosity, which enhances bone regeneration performance. Also provided herein are new biocompatible CaO—Na2O—P2O5—SiO2 glasses prepared by thermal melt-quench methods that result in spinodal phase separation and crystallization of phases at very different length scales. Selective chemical leaching of these phases causes formation of interconnected multi-modal porosity, with pore sizes ranging from several nanometers to tens of micrometers.