Montmorillonite has been treated with Ti-based solutions, alone or doped with Cu2+, Fe3+ or Cr3+ cations, yielding new intercalated solids, which have been calcined at various temperatures to test the stability of the so-formed pillars. The solids calcined at 500°C were fully characterized by chemical analysis, X-ray diffraction, FT-IR spectroscopy, thermal analyses, nitrogen adsorption and acidity evaluation. The evolution of the specific surface area, porosity and acidic properties is discussed, analysing the effect of pillaring and doping procedures on these properties. •Ti-PILC montmorillonites doped with Cu2+, Fe3+ or Cr3+ were prepared.•Doping elements, although in low content, strongly affected polymerization of Ti.•Doped solids were better ordered than undoped pillared montmorillonite.•Specific surface area and acidity were larger in the doped solids.