Ion-molecule reactions involving metallic species play a central role in the chemistry of planetary ionospheres and in many combustion processes. The kinetics of the Ca2+ + N2O -> CaO+ + N-2 reaction was studied by the pulsed multiphoton dissociation at 193 nm of organo-calcium vapor in the presence of N2O, followed by time-resolved laser-induced fluorescence spectroscopy of Ca+ at 393.37 nm (4(2)P(3/2) <- 4(2)S(1/2)). This yielded k(188-1207 K) = 5.45 x 10(-11) (T/300 K)(0.53) exp(282 K/T) cm(3) molecule(-1) s(-1), with an estimated accuracy of +/- 13% (188- 600 K) and +/- 27% (600- 1207 K). The temperature dependence of this barrierless reaction, with a minimum in the rate coefficient between 400 and 600 K, appears to be explained by the role of N2O vibrational excitation. This is examined using a classical trajectory treatment on a potential energy surface calculated at the B3LYP/6-311+g(2d, p) level of theory.