Gas-phase ion/ion reactions between multiply deprotonated DNA and RNA anions and rubrene radical cations have been investigated in this research. Ion/ion reactions of DNA 6-mer (dT 6 , dC 6 , dA 6 and dG 6 ) anions with rubrene radical cations led to negative electron transfer dissociation (nETD), complex formation, and negative electron transfer without dissociation (nET no D). The amount of nET, no D product (G>A>C>T) is inversely related to nucleobase ionization potential (G<A<C<T). On the other hand, the amount of complex formation (G<A<C<T) is positively related to the nucleobase ionization potential, with only minimal complex formation being observed for dG 6 . The nETD channels generally led to the generation of w/d- and a/z-ions, but were only observed when highly deprotonated precursor ions were reacted. Similar trends were observed when reacting RNA 8-mer (rU 8 , rC 8 , rA 8 and rG 8 ) anions with rubrene radical cations (i.e., the yields of nET, no D products (G>A>C>U) and complex formation (G<A<C<U) are inversely related to one another). The major nETD product ions were w/d-ions and a/z-ions, as with the DNA anions, and were only observed at relatively high precursor ion charge states. Furthermore, extensive fragmentation from the w/d- and a/z-ion channels can be obtained from simultaneous activation of the first generation nET, no D survivor radical anions (nET-CID). In comparison to the conventional collisional activation methods, the dissociation of DNA and RNA anions via either nETD or nET-CID is less affected by the structural differences on the 2′-hydroxyl group of the sugar ring.