Reactions of cis-dialkoxy-bis(acetylacetonato)titanium(IV). [(acac)2Ti(OR)2] (R = Et, Pri) with alkoxyalkanols (R′OCH2CH2OH)(R′ = Me, Et, n-Bu) in 1:1 and 1:2 molar ratios in refluxing benzene under anhydrous conditions yield [(acac)2Ti(OR)2-n (OCH2CH2OR′)n] (n = 1 or 2) complexes, which were purified by distillation under reduced pressure. On the basis of i.r. and n.m.r. (1H- and 13C-) spectral studies, a cis-octahedral environment around TiIV is proposed. On keeping the distilled dark brown-red viscous liquid [(acac)2Ti(OEt)(OCH2CH2OBu)] for 2 weeks, orange yellow crystals of [(acac)2Ti(OEt)(OCH2CH2OBu)] were obtained. A single crystal X-ray diffraction study suggests the product is a new modification of [(acac)2TiO]2.