The growth of PSPMA brushes via ARGET was found to be well controlled, even in the absence of inert atmosphere (but with prior degassing of the polymerisation solution), therefore greatly simplifying the protocols used for the controlled polymerisation of this type of brushes. Such conditions should be translatable to a broad range of contexts, beyond the multi-well plate format applied in the current study. Interestingly, the kinetics of PSPMA brush growth via ARGET was found to be enhanced compared to ATRP, in otherwise comparable conditions, perhaps reflecting a lack of control of the precise ratio of Cu(I) to Cu(II) species and associated rates of polymerisation. In turn, the swelling behaviour of PSPMA brushes was found to depend on the density and thickness, but also the catalytic system used. This could indicate that the faster kinetics of brush growth resulting from ARGET leads to more polydisperse, and perhaps sparser, brushes, with increased swelling. However, the chemistry of PSPMA brushes generated via both methods (SI-ARGET and SI-ATRP) was found to be comparable, as confirmed by XPS and FTIR.