Nitrogen-centered radicals (1b., 2b., 3b., 4b.) have been generated upon electron transfer from the corresponding stable nitrenium ions (1b+, 2b+, 3b+, 4b+) and characterized by electrochemistry and simultaneous spectro-electrochemistry. Reactivity of the radicals is strongly influenced by the substituents attached to the two nitrogen atoms that are directly linked to the ion nitrenium center. While 1b. and 2b. are stable on the timescale of the electrochemical experiment, 3b. and 4b. have half-lifetimes of ca. 1.2-1.25 and 0.9-1 μs, respectively, in acetonitrile, as determined with ultramicroelectrodes. Redox properties of the nitrenium ion/radical couples and relative stability of the radicals are discussed in light of both experimental results and ab initio calculations.