We will first describe the choice of starting conditions for the block extension via ATRP. Afterwards, optimal conditions for the addition of 6-7 repeating units of tBAMA via ATRP are shown, followed by an increase of conversion to 40% resulting in well-defined [PEG27-b-PtBAMA41]4 via SET-LRP. Finally, conditions for the deprotection of PtBAMA in a one-pot reaction are found. For the ATRP, optimization of different parameters like the amount of deactivator species, type of copper species, solvent, concentration, temperature, and choices of ligand on Ð and conversion are detailed in the supporting information (Figures ). The choice of ligands used was based on their activity (kATRP) according to literature values. Here, mainly two ligands with different activities were compared: [(2pyridyl)methyl]amine (TPMA) showing higher kATRP and 4,4'-Di-5-nonyl-2,2'-bipyridine (dNbpy) showing lower kATRP considering the activation determined by Robert et al. in 2000. Furthermore, dNbpy was already tested for linear block copolymers, resulting in slow conversion and Đ < 1.4, which rendered dNbpy a promising candidate for our work. Hence, dNbpy will in the following be used for the addition of short segments via ATRP while TPMA is used for higher conversions and longer PDha chains via SET-LRP.