The performance characteristics of two charge-exchange cells (CECs) with horizontal and vertical cell configurations were determined by neutralizing a 10-keV rubidium ion beam in a potassium vapor. The neutralization efficiency and the fluorescence line shape of the 5s2S1/2↔5p2S1/2↔5p2P3/2 (D2) transition in neutral 85Rb were investigated as a function of the reservoir temperature used to control the potassium vapor density. The CECs exhibited similar neutralization performance and at neutralization efficiencies greater than 25–50% an asymmetric line shape of the rubidium D2 fluorescent signal was observed. The asymmetry was attributed to inelastic channels in the charge-exchange process. The rubidium D2 fluorescence line shape was fitted with a multiple Voigt function, which quantitatively models the inelastic channels. In the present Rb+ + K charge-exchange process, the optimum neutralization efficiency to accurately determine the centroid of the Rb D2 resonance line shape was obtained by fitting single Voigt functions to the resonance spectra obtained at neutralization efficiencies where inelastic processes were negligible.