Two novel multifunctional initiators for atom transfer radical polymerization (ATRP) were synthesized by derivatization of tetraethylresorcinarene. The derivatization induced a change in the conformation of the resorcinarene ring, which was confirmed by NMR spectroscopy. The initiators were used in ATRP of tert-butyl acrylate and methyl methaerylate, producing star polymers with controlled molar masses and low polydispersities. Instead of the expected star polymers with eight arms, polymers with four arms were obtained. Conformational studies on the initiators by rotating-frame nuclear Overhauser and exchange spectroscopy NMR and molecular modeling suggested that of eight initiator functional groups on tetraethylresorcinarene, four are too close to each other to be able to initiate the chain growth. Starlike poly(tert-butyl acrylate) macroinitiators were used further in the block copolymerization of methyl methacrylate. (C) 2004 Wiley Periodicals, Inc.