In the present study, different aromatic moieties, naphthalene and benzene, were introduced into alkynes to constitute 1,3,5-tris(naphthylethynyl)benzene as B-3 monomer. This monomer could be reacted with different ratios of hexane-1,6-dithiol (A(2) monomer) via mono-selective Thiol-Yne reaction (TYR) to form hyperbranched polymers PI. TYR yielded in both, model reactions and polymerizations, monoadducts with high regioselectivity and proved the absence of any bis-adducts. Polymers of very high molecular weights of up to 625,000 g/mol could be achieved without any sign of gel formation. All the polymers exhibit high transparency in the visible wavelength range and also show high refractive indices of up to 1.745 at 589.7 nm due to the high incorporation of naphthalene and phenyl groups. Besides, all polymers prove excellent solubility and processability together with excellent thermal properties. (C) 2014 Elsevier Ltd. All rights reserved.