Long-lived ligand-to-metal charge transfer (LMCT) excited states based on a zirconium complex (ca. 2000 mus) and a hafnium complex (ca. 300 mus) are first characterised with use of the Cp2Zr(IV)Cl-2 and Cp(2)Kf(N)Cl-2. The tendency in the observed photoyhysics (absorption and phosphorescence spectra, lifetimes, and quantum yields) in the homologous group NE metallocenes Cp2M(IV)Cl-2 is discussed in view of the nature of the unique metal (Ti, Zr or Hf)-ligand pi -bonding character.