By using the Scheutjens−Fleer self-consistent field approach, the structure of the fourth-generation dendrimer with attached terminal chemically different oligomeric segments is studied theoretically. It is demonstrated that an incompatibility of terminal segments with inner dendrimer units leads to formation of a “hollow” core with reduced polymer density in the dendrimer center. This effect is enhanced with a deterioration in the solvent quality for terminal segments. This observation is in accordance with experimental results and molecular dynamics simulation data for an analogous system. It is established that the main factor determining the hollow core formation is the segregation between inner and terminal units because the main driving force for the effect is the localization of the terminal segments at the dendrimer periphery. The influence of structural parameters of dendrimer such as the number of generations and length of the terminal chain on this effect is also studied.