Vacuum UV fluorescences from ionic alkali-halide and rare-gas alkali excimers were observed by e-beam excitation. The two diffuse emissions centered at 185 and 154 nm from the CsF vapor were attributed to the bound-free B2Σ+ → X2Σ+ and D2Π → X2Σ+ bands of (CsF)+, respectively. And, the 164- and 133-nm diffuse bands from gas the mixture of Xe or Kr with hot vapor of Rb were assigned to the emissions of (XeRb)+ and (KrRb)+ ionic excimers. In addition, amplified spontaneous emissions of the Na2 violet, K2 yellow, and Rb2 orange diffuse bands were observed from e-beam-excited alkali vapor with argon buffer gas. The continuum spectra centered at 436, 574, and 604 nm were attributed to triplet-triplet Na2, K2, and Rb2 23Πg → 13Σu+ bound-free transitions, respectively. The dissociative recombination of Na3+, K3+, or Rb3+ is discussed as an efficient formation process of the upper states in e-beam pumping.