The orange-colored and hydrolytically stable compound {[Ti₂O(bhmpc)(Hbhmpc)(H₂bhmpc)].C₄H₈O₂.HX}₂ (with H₃bhmpc = 2,6-bis(hydroxymethyl)-p-cresol and X = OEt or CCl₃) has been studied by a combination of single crystal X-ray diffraction data, U.V.-vis. spectroscopy, IR and Raman spectroscopies, ¹H, ¹³C and ¹⁷O solution NMR spectroscopies, electron density and statistical thermodynamics modeling. We observed that the molecular structure found in the solid state is conserved in solution. Based on X-ray diffraction data, we also propose a complete and non-ambiguous assignment for the fully resolved ¹H and ¹³C solution NMR spectra through the use of 2D-techniques (COSY, ROESY, HSQC, HMBC) and ¹H relaxation time measurements. The ability of the partial charge model introduced more than 20 years ago by J. Livage’s group to reproduce observed ¹³C NMR chemical shifts in solution is demonstrated. Statistical thermodynamic modeling between Ti(OR)₄ (monomers, trimers or tetramers) has shown that complexation was in all cases under entropy control. Possible applications of this soluble and stable precursor to the sol–gel processing of hybrid organic–inorganic are addressed.