The photochemistry of Urocanic acid, a chromophore present in human skin and linked to photoimmunosuppression and skin cancer, is investigated theoretically by means of time-dependent density functional theory. Extensive calculations are carried out for different ionic, rotameric, and protomeric forms of both the trans and cis form. Inclusion of solvation effects, here accounted for by means of a continuum solvent model, are found to be crucial for the correct description of the biologically relevant zwitterionic forms of the molecule. For the trans zwitterionic form, it is found that the planar form usually assumed in the literature is not stable, and that a realistic charge separation cannot be achieved in the gas phase. Calculated vertical excitation energies are in excellent agreement with available experimental data, with a weakly absorbing n --> pi* transition around 4.0 eV, and strongly absorbing pi --> pi* transitions at 4.5-4.9 eV. The debated intramolecular hydrogen bond is predicted to have a modest impact on the vertical spectra in solution, but improves agreement with experiment when included. In general, we also predict that different rotameric forms have very similar absorption spectra. In addition, we find a candidate absorbing state to link trans-urocanic acid to singlet oxygen production and subsequent photoaging of the skin.