Vibrational deactivation and charge transfer in the collisions of N-2(+)(nu = 0-4) With N-2 and O-2 are studied at thermal energies. State-specific rate constants for the individual components of charge transfer and vibrational deactivation are determined using the selected-ion flow tube, laser-induced fluorescence technique. The N-15(2)+(nu = 0) + N-14(2) reaction proceeds via symmetric charge transfer at one-half the Langevin rate constant (0.5k(L)), indicating efficient charge equilibration, whereas the total removal rates of nu = 1-4 (similar to 6 x 10(-10) cm(3) molecule(-1) s(-1)) exceed 0.5k(L). This indicates that vibrational transfer, in addition to charge equilibration, contributes to the removal of N-2(+)(nu > 0) by collisions with Nz. The N-2(+)(nu) + O-2 removal rates are significantly enhanced upon vibrational excitation; the total rate constant for nu = 4 is 3.0 x 10-(10) cm(3) molecule(-1) s(-1), six times larger than that for nu = 0. The enhancement is shown to be primarily due to increased vibrational deactivation, although a small enhancement of the charge-transfer channel also occurs for N-2(+)(nu greater than or equal to 2) + O-2. Multiquantum vibrational energy transfer during single collisions plays an important role in the deactivation of N-2(+)(nu greater than or equal to 2) with both N-2 and O-2. The occurrence of multiquantum deactivation is rationalized by the existence of significantly deep potential wells for N-2(+)-N-2 and N-2(+)-O-2, which arise from electron-exchange interactions. Small modifications are also made to the earlier studies on the reactions of N-2(+)(nu greater than or equal to 2) + N-2 (Frost, M. J.; et al. J. Chem. Phys. 1994, 100, 6359) and N-2(+)(nu greater than or equal to 2) + O-2 (Kato, S.; et al. Can. J. Chem. 1991, 72, 625).