In the present work, Bismuth- Sodium-Barium Titanate (BNBT) electroceramics were prepared by mechanical alloying (MA) and their structure, microstructure, chemical composition and thermal behavior were investigated by XRD, SEM, EDX, DTA/TG, respectively. The XRD results indicated that the peaks related to the primary materials are disappeared at initial milling times and after sufficient milling time (150 h) the BNBT perovskite phase is appeared. By continuation of milling to 300 h the perovskite phase almost totally developed. In addition, due to the peak broadening at 2q higher than 35 (particularly at 150 h of milling), the presence of a considerable amount of amorphous phase is obvious in the structure. The microstructural analysis revealed that, by progression of milling, the powder particle size is reduced continuously and the equiaxed morphology is developed. Furthermore, chemical composition assessment demonstrated that the desirable distribution of elements has been accomplished by development of MA. Moreover, the presence of the amorphous and perovskite BNBT phases was confirmed by thermal analysis.