The synthesis of fourth-generation bola-type linear-dendritic macromolecules is described using a high yielding divergent method. These systems are composed of a non-immunogenic linear poly(ethylene glycol) core and dendritic wedges of succinic acid and glycerol connected by ester linkages in a triblock architecture. Three molecular weight PEGs (3400, 10 000, and 20 000 g/mol) were used in the synthesis of low, medium, and high molecular weight macromolecules. The molecular weight data were determined by MALDI-TOF and SEC. The macromolecules were further characterized by modulated differential scanning calorimetry (MDSC) and critical aggregation concentration (CAC) as determined by fluorescence spectroscopy. Cell toxicity studies were performed with human umbilical vein endothelial cells (HUVEC). These macromolecules are of interest for a variety of biomedical applications including the repair of ocular wounds. © 2006 American Chemical Society.