The methods of infrared (IR) spectroscopy and Raman spectroscopy (RS) are herein used to characterize the features of the surface state of Ti3C2Tx (T = OH–, O2–, F–) layered materials obtained in the form of powder and two-dimensional (2D) particles forming a stable colloidal solution. A powdered sample of Ti3C2Тх is obtained by removing aluminum from Ti3AlC2 by treatment in an HF solution, 2D Ti3C2Тх particles are obtained by treating Ti3AlC2 in an HCl+LiF solution followed by sonication. The phase composition and morphology of the samples are studied by X-ray diffraction and electron microscopy. The IR and Raman spectroscopy methods permitted to differentiate the presence of terminal groups (O2–, OH–, F–) of various nature with a quantitative predominance of the OH form in the Ti3C2Tx powder sample and OH and fluoride ions in 2D Ti3C2Tx particles, and also detect the presence of TiOx impurities.