A new method of synthesis of advanced hydrated metatitanate pseudomorphs obtained via extraction of sulfate ions from the crystals of titanyl sulfate dihydrate and their replacement with hydroxyl groups of NaOH, LiOH and KOH solutions leaving the Ti-O framework untouched has been proposed. The resulting materials exhibit specific structural properties, which were determined by a number of methods, including scanning and transmission electron microscopy, X-ray diffraction and thermal analysis coupled with mass spectrometry. It was observed that while material precipitated by KOH is thermally stable up to 150 °C, the decomposition of LiOH and NaOH materials starts right at the beginning of the heating. With the increasing temperature, the amorphous materials start to crystallize into various lithium, sodium and potassium titanates and furthermore the growth of larger crystals and nanowhiskers on rods during the crystallization process was observed and discussed.