The crystallization behaviors of As–Se–Bi chalcogenide glasses were investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). Three models were used to study the glass transition behavior and the activation energy. Results showed thermal stability of glass against crystallization decreased with Bi addition in As–Se–Bi system. The mechanism of crystal growth in glasses was also studied by the Avrami exponent n. For B0, B2.5, and B5, n values are 3.12, 1.59, and 2.21 (low temperature) and 4.61 (high temperature), respectively. The thermal stability of glass is in good agreement with glass network structure. It was found that glass network structures closely associated with the Bi content and As/Se ratio were studied by X‐ray diffraction and Raman spectroscopy. And the different ratios lead to the change in Bi2Se3 crystalline orientation.