Proflavine, a fluorescent cationic dye with strong absorption in the visible, has been proposed as a potential contributor to diffuse interstellar bands (DIBs). To investigate this hypothesis, it is essential to examine the spectra of cold and isolated ions for comparison. Here, we report absorption spectra of proflavine ions, trapped in a liquid-nitrogen-cooled ion trap filled with helium-buffer gas, as well as fluorescence spectra to provide further information on the intrinsic photophysics. We find absorption- and fluorescence-band maxima at 434.2 ± 0.1 and 434.7 ± 0.3 nm, corresponding to a Stokes shift of maximum 48 cm⁻¹, which indicates minor differences between ground-state and excited-state geometries. Based on time-dependent density functional theory, we assign the emitting state to S₂ as its geometry closely resembles that of S₀, whereas the S₁ geometry differs from that of S₀. As a result, simulated spectra involving S₁ exhibit long Franck-Condon progressions, absent in the experimental spectra. The latter displays well-resolved vibrational features, assigned to transitions involving in-plane vibrational modes where the vibrational quantum number changes by one. Dominant transitions are associated with vibrations localized on the NH₂ moieties. Experiments repeated at room temperature yield broader spectra with maxima at 435.5 ± 1 nm (absorption) and 438.0 ± 1 nm (fluorescence). We again conclude that prevalent fluorescence arises from S₂, i.e., anti-Kasha behavior, in agreement with previous work. Excited-state lifetimes are 5 ± 1 ns, independent of temperature. Importantly, we exclude the possibility that a narrow DIB at 436.4 nm originates from cold proflavine cations as the band is redshifted compared to our absorption spectra.