1,1-Diphenylethylenene (DPE) was copolymerized anionically with styrene to yield well-defined alternating copolymers, which were terminated by reacting the "living" polymeric carbanion species with 4'-chloro-2,2':6'2"-terpyridine. DPE containing polymers show improved long-term service temperatures due to the stiffening of the polymer main chain by the bulky phenyl-rings. In addition, the functionality provided by the terpyridine group allows the synthesis of attractive materials for various fields of application. The obtained polymers were fully characterized by means of nuclear magnetic resonance, gel permeations chromatography, elemental analysis, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, ultraviolet-visible spectroscopy, and macromolecular hydrodynamic methods (analytical ultracentrifugation, gel permeation chromatography, intrinsic viscosimetry). In the molar mass range of 2 < M < 25 kg/mol, the scaling relationships between M and hydrodynamic characteristics are obtained. The values of the Kuhn segment length (or persistence length) and hydrodynamic diameters Eire evaluated and compared with those of linear polystyrene. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3691-3701, 2009