TlC5H5 displays absorption maxima at 228 and 280 nm which are assigned to metal-centred sp and ligand-to-metal charge transfer (LMCT) transitions, respectively. The complex shows an emission at λmax = 360 nm which originates from a low-energy sp excited state. The photolysis of TlC5H5 in methanol proceeds according to the equation TlC5H5 + CH3OH → TlOH + H2 + C6H6 (pentafulvene) with φ = 0.1 at λirr = 254 nm and 0.008 at 313 nm. It is suggested that this photoreaction is induced by LMCT excitation.