A series of well-defined linear polystyrenes (PSs) with different degree of polymerization (DP) was synthesized via atom transfer radical polymerization (ATRP) using tert-butyloxycarbonyl (t-boc)-protected 4-(aminomethyl) phenyl 2-bromoisobutyrate (BAPB) as an initiator. The resulting polymers were deprotected by cleavage of the t-boc protecting groups via treatment with trifluoroacetic acid (TFA) to generate the chain-end primary amine functionality. The chain-end primary amine groups of the polymers were self-coupled in the presence of 2,2'-azobisisobutyronitrile (AIBN) under an oxygen atmosphere via imine bond formation. The coupling efficiency decreased slightly as the chain length of the PS increased. The imine linkages of the coupled PSs were hydrolyzed in the presence of HCl to individual PS chains. (C) 2015 Elsevier Ltd. All rights reserved.