In the paper, modeling experiments on nanoclusters segmentation process are considered. The modeling is performed in the software package “Gaussian’03” with the Electron density functional theory approach. It is demonstrated that even metastable flat shape of Ti₅C₄ and Ti₄C₅ types can spontaneously form Ti₁₄C₁₃ and Ti₁₃C₁₄ nanoclusters of different shapes depending on distance and relative orientation of available surfaces. If the surfaces are adjacent to each other then cubic nanoclusters are formed. A relatively large shift forms nanoclusters of «bucket» and «dimer» type. Initially, the segmentation is dependent on a long-range interaction between metal atoms of different surfaces. After a “skeleton” of metal atoms is created, the Ti–C bonding occurs, and final configuration is formed. Cubic nanoclusters Ti₁₄C₁₃ and Ti₁₃C₁₄ are appeared to be more stable than the non-cubic ones with the lowest stability of Ti₁₃C₁₄ with the “bucket” form.