We studied amorphous lead titanium alkoxide-derived heterometallic complexes, prepared from lead acetate and titanium n-propoxide or n-butoxide in parent alcohol medium. According to gas-liquid chromatography (GLC) and thermogravimetric analysis with mass spectrometry of evolved species (TGA/EGA) analyses, the type of alkoxide group influences oxo or acetate bridging, as well as the amounts of hydroxyl and organic groups bound to the metal network. From XANES and EXAFS analysis, local environments of lead and titanium atoms were determined within the analyzed range of 3.4 Å. Local environments depend weakly on the type of alkoxide used. Titanium atoms are pentacoordinated. A Pb–Ti correlation is established with lead atoms bound to titanium atoms by oxygen linkages.