The Savannah River National Laboratory (SRNL) developed a new geometric form: hollow glass microspheres (HGMs), with unique porous walls. The new geometric form combines the existing technology of HGMs with basic glass science knowledge in the realm of glass in glass phase separation. Conceptually, the development of a HGM with porous walls (referred to as a PWHGM) provides a unique system in which various media or filling agents can be incorporated into the PWHGM (via transport through the porous walls) and ultimately has the capacity to serve as a functional delivery system in various industrial applications. Applications of these types of systems could range from hydrogen storage, molecular sieves, drug and bioactive delivery systems, to environmental, as well as chemical and biological indicators, relevant to Energy, Environmental Processing and Homeland Security fields. As a specific example, previous studies at SRNL have introduced materials capable of hydrogen storage (as well as other materials) into the interior of the PWHGMs. The goal of this project was to determine if the microstructure (i.e., pore size and pore size distribution) of a PWHGM could be altered or tailored by varying composition and/or heat treatment (time and/or temperature) conditions. The ability to tailor the microstructure through composition or heat treatments could provide the opportunity to design the PWHGM system to accommodate different additives or fill agents. To meet this objective, HGMs of various alkali borosilicate compositions were fabricated using a flame forming apparatus installed at the Aiken County Technical Laboratory (ACTL). HGMs were treated under various heat treatment conditions to induce and/or enhance glass in glass phase separation.