Initiators for atom transfer radical polymerization (ATRP) bearing different functional groups (aldehyde, aromatic hydroxyl, dimethyl amino) were synthesized and characterized. Monotelechelics with low molecular weight were obtained by ATRP of styrene using these initiators in the presence of the CuBr/bpy catalytic complex. alpha,omega-Telechelic polymers with double molecular-weights with respect to the starting materials were prepared by coupling of monotelechelics under atom transfer radical generation conditions, in the absence of monomer, using CuBr as catalyst, tris[2-(dimethylamino)ethyl]amine (Me6TREN) as a ligand, under Cu-0 mediated reductive conditions and with toulene as solvent. Terminal Br atoms present in monotelechelic polystyrenes (PS) as a consequence of the ATRP mechanism also offer other routes for preparing telechelic polymers. Aldehyde functionlized polymer was etherified with hydroquinone furnishing telechelic PS with a molecular weight that was two times higher. All polymers were characterized by spectral methods (NMR, IR spectroscopy) as well as by CPC.