In this work, we present the synthesis of well-defined double hydrophilic star-shaped block copolymers poly(ethylene glycol)-block-polydehydroalanine [PEGx-b-PDhay]4, with either short (6-7 repeat units) or longer arms (~ 40 repeat units) for the ampholytic segment. While PEG offers high-water solubility, PDha as weak polyampholyte is either positively charged, negatively charged, or zwitterionic depending on the solution pH value and, with that, our aim was to study the influence of short charged segments on the solution behavior of such materials. As both oppositely charged moieties are carried in the same monomer unit PDha can further be defined as polyzwitterion. In 2013 Günther et al. compared free radical polymerization with NMP for the polymerization of tert-butoxycarbonylaminomethyl acrylate (tBAMA) and investigated afterwards the deprotection reaction of PtBAMA to obtain PDha. Furthermore, in 2016