The ion-ion neutralization reactions of NO+(X (1) Sigma(+):upsilon "=0) with C6F5Cl-, C6F5Br-, and C6F5- have been spectroscopically studied in the flowing helium afterglow. The NO(A (2) Sigma.-(+) X (2) Pi(r), C (2) Pi(r)-X (2) Pi(r), D (2) Sigma(+)-X (2) Pi(r)) emission systems are observed in the NO+/C6F5Cl- reaction with the branching ratios of 0.96, 0.017, and 0.028, respectively, while only the NO(A -X) emission system is found in the NO+/C6F5Br- and NO+/C6F5-; reactions. The vibrational and rotational distributions of NO(A,C,D) indicate that only 1%-11% of the excess energy is deposited into vibration and rotation of NO(A,C,D) for all the reactions. In the NO+/C(6)F(5)X(-) (X=Cl,Br) reactions, a major part of the excess energy is expected to be partitioned into the relative translational energy of the neutral products and the vibrational energy of C(6)F(5)X. A comparison of the observed vibrational and rotational distributions with the statistical prior ones indicates that the reaction dynamics is not governed by a simple statistical theory because of the large impact parameter. The excitation mechanism of NO(A,C,D) in the ion-ion neutralization reactions of NO+ with C(6)F(5)X(-) (X=F,Cl,BT,CF3) and C6F5- is discussed.