Hollow nanospherical bioactive glasses were conducted though sol–gel process using poly(acrylic acid) (PAA) as the template. The incorporation of PAA was to form the core after air combustion, whereas the inorganic shell was produced by glass precursor. The mixture of different tetraorthosilicate (TEOS)/PAA contents into a glass network tailored the shell thickness, morphological, and structural properties of HBGs. The in vitro bioactivity evaluation confirmed that HBG2 sample exhibited good apatite formation ability, thereby denoting that the proposed method enhanced the potential application of HBGs in bone tissue regeneration and drug delivery.