Poly(2-(methacryloyloxy)ethyl phosphorylcholine) [PMPC] is a highly biocompatible zwitterionic polymer. PMPC brushes prepared by surface ATRP offer high aqueous lubricity and the protein resistance of PMPC-coated surfaces increases greatly with grafting density. Our group has recently demonstrated the use of polyelectrolyte macroinitiators for surface-initiated ATRP. These macroinitiators can be synthesised more easily and on a much larger scale than silane initiators, and can replace them for surface ATRP from many substrates. In addition, silanes are usually incompatible with water, whereas macro-initiators can be successfully used to functionalize water-borne substrates (such as silica sols). We present the surface ATRP of PMPC from planar oxidized silicon using polyelectrolyte macro-initiators in either methanol or methanol/water mixtures at ambient temperature. In methanol, well-controlled slow growth up to 120 nm was observed, whereas ultra-thick films up to 500 nm could be grown rapidly in methanol/water mixtures. Growth of diblock copolymer brushes of PMPC with poly(2-(diisopropylamino)ethyl methacrylate) [PDPA] is also demonstrated and their surface properties are investigated. We also present the growth of cross-linked PMPC brushes prepared using ethylene glycol dimethacrylate (EGDMA) as a comonomer. Films consisting of a cross-linked underlayer and a non-cross-linked overlayer have been recently suggested to offer superior lubricity, since such coatings provide mobile chains to enhance lubrication while preventing asperity penetration. Thus we have synthesised diblock copolymer brushes (PMPC/EGDMA-b-PMPC) to test this hypothesis. The analogous diblock copolymer brushes cross-linked using a disulfide-based dimethacrylate (DSDMA) comonomer were also prepared. The disulfide bonds in DSDMA act as branch points that can be readily cleaved by the addition of a mild reducing agent such as dithiothreitol (DTT), which may allow the cross-links to be cleaved in situ during testing. Macroinitiators are particularly useful for surface ATRP from high surface area substrates, since their synthesis can be readily scaled-up. We present results of PMPC growth from 13 µm diameter quartz fibres with a specific surface area of 0.14 m²g^-1. This value is intermediate between those typical of planar silicon wafers (10^-3 m² g^-1) and colloidal particles (e.g. 19 m²g^-1 for a 300 nm polystyrene latex or 140 m²g^-1 for a 20 nm silica sol). We hope that this new model substrate, combined with brush degrafting techniques, will provide sufficient quantities of degrafted polymer brush chains for GPC analysis, without suffering the curvature effects that characterize brush growth from colloidal substrates. These PMPC-based brushes were characterized using ellipsometry, XPS, contact angle goniometry, FTIR spectroscopy and AFM.