Infrared spectra of codeposited ethyl benzoate with excess titanium tetrachloride at 80 K revealed a novel 2:1 complex, where the inorganic entity is proposed to be a dimeric, triple bridged titanium tetrachloride unit. The ester is complexed to one of the octahedral titanium units through the carbonyl group. Compared to the 2:2 complex there are νc=o'να-C-Oand νTi-Oshifts of -40/-47, +4/+24 and +16/17 cm−1, depending on which of the18O-carbonyl or d5-ethyl isotopic congeners is considered.