A series of 3 homologous surface-anchored initiators for atom transfer radical polymerization has been used to graft linear, Y- and Ψ-shaped poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(methyl methacrylate) (PMMA) brushes from silicon surfaces. The film thicknesses of these architecturally different polymer brushes could be tuned both by controlling the polymerization time, as well as (as was shown for the polymerization of 2-(dimethylamino)ethyl methacrylate) by changing the monomer concentration. The library of linear, Y- and Ψ-shaped PDMAEMA and PMMA brushes was used to investigate the possible impact of polymer architecture on the swelling properties as well as the degrafting behavior of these surface-grown polymer films. The swelling of the PDMAEMA and PMMA brushes in PBS, respectively, acetone as a solvent was studied by ellipsometry. These experiments revealed a smaller swelling ratio for Y-shaped polymer brushes, as compared to linear analogues of comparable dry film thickness. Degrafting experiments were conducted with linear, Y- and psi-shaped PDMAEMA brushes in PBS. These experiments revealed a 2-fold, respectively, 3-fold increase in the initial rate constant of degrafting for the Y- and Ψ-shaped PDMAEMA brushes as compared to the linear analogues.