Abstract: A new method for producing electronically excited nitrogen monohalides NX(b) (X=F,Cl,Br) is reported. The strong emission spectra of NBr(b1Σ+→X3Σ–) are observed when alkyl bromides (CHBr3, CH2Br2, C2H5Br, and C4H9Br) are added to a stream of active nitrogen, generated by a hollow-cathode discharge of N2, in a flowing afterglow system. Some tentative experiments show that the electronically excited NBr(b) is formed by means of metastable N2(A3Σu+) Electronic-to-Electronic energy transfer to NBr(X), which is from the reaction of N(4S) with alkyl bromides. The emission spectra of NCl(b1Σ+→X3Σ–) are obtained when CCl4 or SOCl2 is admitted into a flow of active nitrogen, but neither CHCl3 nor CH2Cl2 addition results in such an emission. It has been proposed that the origin of the excited NCl(b) is an energy transfer from N2 (A) to NCl(X), generated by the reaction of N(4S) with CCl3 (or SOCl2). Similar experiments are also carried out with SF6 as reagent of active nitrogen, or as mixture with N2 in the discharge. By recording fluorescence it was found that excited NF(b) is produced only under discharge through N2/SF6 mixture. The NF(b) state presumably arises from the energy transfer from N2(A) to NF(X), and the latter is generated from the abstraction of fluorine by N(4S) from SF5.