As it has been established that boron (B) may perform functions in angiogenesis and osteogenesis, the controlled and localized release of B ions from bioactive glasses (BGs) is expected to provide a promising therapeutic alternative for regenerative medicine of vascularized tissues, such as bone. The aim of this study was to assess the in vitro angiogenic effects of the ionic dissolution products (IDPs) from BGs in the SiO2-CaO-Na2O-P2O5 (45S5) system and of those from 45S5 BG doped with 2 wt% B2O3 (45S5.2B). The results show, for the first time, the IDPs from 45S5.2B BG stimulated human umbilical vein endothelial cell (HUVEC) proliferation and migration that were associated with phosphorylation of extracellular signal-related kinase (ERK) 1/2, focal adhesion kinase (FAK) and p38 protein. It was also shown that IDPs from 45S5.2B BG could enhance in vitro HUVEC tubule formation and secretion of interleukin 6 (IL6) and the basic fibroblast growth factor (bFGF). The effects observed are attributed to the presence of B in the IDPs. These findings are relevant to bone tissue engineering and regeneration because the IDPs from 45S5.2B BG may act as inexpensive inorganic angiogenic agents providing a convenient alternative to the application of conventional angiogenic growth factors.