The UV photofragmentation spectra of cold cytosine-M+ complexes (M+: Na+, K+, Ag+) were recorded and analyzed through comparison with geometry optimizations and frequency calculations of the ground and excited states at the SCS-CC2/Def2-SVPD level of theory. While in all complexes, the ground state minimum geometry is planar (C-s symmetry), the pi pi* state minimum geometry has the NH2 group slightly twisted and an out-of-plane metal cation. This was confirmed by comparing the simulated pi pi* Franck-Condon spectra with the vibrationally resolved photofragmentation spectra of CytNa+ and CytK+. Vertical excitation transitions were also calculated to evaluate the energies of the CT states involving the transfer of an electron from the Cyt moiety to M+. For both CytK(+) and CytNa(+) complexes, the first CT state corresponds to an electron transfer from the cytosine aromatic pi-ring to the antibonding sigma* orbital centered on the alkali cation. This pi sigma* state is predicted to lie much higher in energy (>6 eV) than the band origin of the It pi-pi* electronic transition (around 4.3 eV) unlike what is observed for the CytAg(+) complex for which the first excited state has a n(O)sigma* electronic configuration. This is the reason for the absence of the Cyt(+) + M charge transfer fragmentation channel for CytK(+) and CytNa(+) complexes.