Bioactive glass (BG) is considered to be one of the most remarkable materials in the field of bone tissue regeneration due to its superior bioactivity. In this study, both un-treated and polyethylene glycols (PEG)-treated BG particles were prepared using a spray pyrolysis process to study the correlation between particle morphology and degradation behavior. The phase compositions, surface morphologies, inner structures, and specific surface areas of all BG specimens were examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption/desorption, respectively. Simulated body fluid (SBF) immersion evaluated the assessments of bioactivity and degradation behavior. The results demonstrate three particle morphologies of solid, porous, and hollow factors. The correlation between porosity, bioactivity, and degradation behavior was discussed.