Aminooxy alpha- and alpha,omega-end-functionalized polystyrene were synthesized via atom transfer radical polymerization (ATRP) and atom transfer radical (ATR) coupling. A 1-bromoethylphenyl initiator possessing an N-hydroxyphthalimide group was used for copper-mediated ATRP of styrene. The polymerization kinetics indicated good control with high initiator efficiency, and the resulting polymers had polydispersity indices (PDIs) as low as 1.12. N-Hydroxyphthalimide-polystyrene was then dimerized using Cu(0)-mediated ATR coupling, and GPC results indicated high coupling efficiency. Hydrazine deprotection of both the alpha and alpha,omega-end-functionalized polystyrene to the aminooxy groups was confirmed by H-1 NMR spectroscopy. End-group reactivity was verified by reaction with 4-bromobenzaldehyde to form the oxime linkages.