The complex [Ti(2,4-dimethyl-2,4-pentanediolate)(2)](2) (1) has been synthesized from [Ti((OPr)-Pr-i)(4)] by transesterification with a stoichiometric amount of 2,4-dimethyl-2,4-pentanediol, We have characterized complex 1 in the solid state by single-crystal X-ray diffraction and in the gas phase by desorption chemical ionization mass spectrometry (DCI-MS). The structural and mass spectrometric data show complex 1 to be stable as a dimer in both the solid and gas phases. The retention of dimeric nuclearity in the gas phase sets complex 1 apart from other simple titanium alkoxide complexes [Ti((OPr)-Pr-i)(4)] and [Ti(OMe)(4)](4) that give rise to respective families of molecular ions in the DCI-MS experiment. The highest mass molecular ions for Ti alkoxide complexes in the gas phase may reveal the highest nuclearity that these complexes achieve in condensed phases. According to this interpretation the complex [Ti((OPr)-Pr-i)(4)] is principally dimeric in the gas phase and probably also in the pure liquid phase and should be represented by the formula [Ti((OPr)-Pr-i)(4)](2).