As a new kind of energy‐saving glass, vacuum glazing has excellent thermal and sound insulation properties and is widely used in building, household appliances and solar photovoltaic. The edge sealing material, along with sealing method, is key to the fabrication of vacuum glazing. Low transition temperature (Tg) and good fluidity at sealing temperature (Ts) make low‐melting glass of V2O5–TeO2–Bi2O3 (VTB) system perfect to be the edge sealing material for vacuum glazing. The glass forming region of VTB ternary system was mapped for the first time in this work. Low‐melting VTB glass of 40V2O5–50TeO2–5Bi2O3–3ZnO–2Na2O (wt%) was optimized to be the sealing material. Glass powder of this composition could be used to seal the edges of vacuum glazing at an extremely low temperature of 360°C. With the assistance of anodic‐bonding method, the bonding strength of vacuum glazing was dramatically enhanced. Vacuum glazing fabricated under the optimized process parameters of 420°C, 600 V, and 60 min possesses a highest bonding strength of 4.31 MPa. Furthermore, anodic‐bonding mechanism of low‐melting VTB glass applied in vacuum glazing sealing has been thoroughly researched.