(Titanium)(n)(benzene)(m)(-) cluster anions were studied by both mass spectrometry and anion photoelectron spectroscopy. The cluster anion series, Ti-n(Bz)(n+1)(-), (n = 1-6) dominated the mass spectra. Vertical detachment energies and adiabatic electron affinities were determined for (n,m) = (1,1), (1,2), (2,3), (3,4), (4,5), and (2,4). The evidence suggests that members of the Ti-n(Bz)(n+1)(-) series have multiple-decker sandwich structures. Ti-2(Bz)(4)(-) was observed and appears to be the dimer anion, (Ti(Bz)(2))(2)(-). (C) 2004 Elsevier B.V. All rights reserved.