The Cu(0)-mediated polymerization of lauryl (C12) and stearyl (C18) acrylate is reported under a range of reaction conditions. Good first order kinetics, a linear evolution of number average molecular weight (Mn) with conversion and dispersity (∼1.10) are observed. The polymerization of lauryl acrylate proceeds either homogenously or in a self-generated biphasic system, depending on the solvent employed, with little deviation in overall polymerization control. The near quantitative retention of ω-bromo end groups is exploited via nucleophilic thio-bromine substitution with thioglycerol to yield highly hydrophobic polymers with polar head groups. Modification is spectroscopically confirmed by both NMR and MALDI-TOF-MS. Highly ω-chain end functional methacrylic analogues have also been prepared by Co(II) mediated catalytic chain transfer polymerisation (CCTP). Reactive vinyl groups at the ω-chain end of poly(lauryl methacrylate) have been targeted with thioglycerol for nucleophilic thio-Michael addition with quantitative modification possible.