Abstract: The emission spectra of BiO(A ~2Π_(1/2)) have been first obtained by studying the reaction Bi+N_2O in the heat pipe oven. 18 new bands are obtained from the emission spectra of BiO(A ~2Π_(1/2)) which are attributed to the reaction of atomic Bi~*(~2D_(3/2)) with N_2O(~1Σ_g~+). The metastable Bi~*(~2D_(3/2)) is produced by the following processes: Bi(~4S_(3/2))+N_2O(~1Σ_g~+)→BiO(X_2~2Π_(3/2)), and then,BiO(X_2~2Π_(3/2))+Bi(~4S_(3/2))→Bi~*(~2D_(3/2))+BiO(X_1~2Π_(1/2)).