Here we report on the synthesis of dumbbell-like linear–dendritic copolymers based on polyethylene glycols bearing aspartic dendrons with terminal amino and carboxylic groups. The ionic complexes of such oppositely charged copolymers demonstrate the ability to self-assemble in water and methanol and form gels in low polar solvents. Differential scanning calorimetry, polarizing optical and atomic force microscopy, and X-ray diffraction methods indicate a lamellar structure of PEG-copolymer complexes. The thickness of the layers, degree of order, and crystallinity of the PEG microphase are determined by the structure of the branched block.