The synthesis and crystallographic characterization of alkali-metal-doped ethoxotitanate clusters with 28 and 29 Ti atoms as well as a new dopant-free Ti-28 cluster are presented. The light-metal-doped polyoxotitanate clusters in which the alkali-metal atom is the critical structure-determining component are the largest synthesized so far. Calculations show that doping with light alkali atoms narrows the band gap compared with the nondoped crystals but does not introduce additional energy levels within the band gap.