 The TiO2(B) and TiO2(rutile) polymorphs are often contaminated by anatase phase residues from synthesis. The detection of anatase in TiO2 material can be difficult in case of small anatase impurities. In situ Raman spectroelectrochemistry is presented here as the most reliable method for unequivocal determination of anatase phase in TiO2 powder. Anatase detection is based on an occurrence of Raman vibrational bands of orthorhombic lithium titanate, a product of Li insertion in anatase, in Raman spectra of TiO2(B) and TiO2(rutile) materials during electrochemical Li+ insertion/extraction.