Our objective was the precision synthesis of novel stars consisting of a well-defined calix[8]arene core out of which radiate eight poly(isobutylene-aze-styrene) [P(IB-aze-St)] arms fitted with crosslinkable end groups. We reached our objective by preparing the octafunctional calixarene derivative C[8]OCH3, inducing the living azeotropic copolymerization of IB/St charges with the C[8]OCH3/BCl3. TiCl4 initiating system, and end-quenching living IB/St copolymerizations with allyltrimethylsilane. With this strategy, we obtained stars C[8]-[P(IB-aze-St)-CH2CH=CH2](8) of various molecular weights. The number of -CH2CH=CH2 termini of the arms was 8.0 +/- 0.2 by quantitative H-1 NMR analysis. The eight allyl termini were quantitatively converted to -CH2CH2CH2OH termini by hydroboration/oxidation. To cofirm that the latter second-generation stars possessed eight primary alcohol end groups, we quantitatitely converted the -CH2OH termini to -OSi(CH3)(3) termini, the concentration of which was quantitated by H-1 NMR spectroscopy. According to this analysis, the stars contained 8.0 +/- 0.3 hydroxyl termini. The glass-transition temperatures of the P(IB-aze-St) arms increased from 59 to 65 degreesC as the weight-average molecular weights of the arms increased from about 2500 to about 4300 g/mol, respectively. The alpha and K constants of the Mark-Houwink-Sakurada relationship and the intrinsic viscosity of a representative allyl-telechelic star were determined and compared with a linear azeotropic IB/St copolymer of similar molecular weight. The crosslinking of C[8]-[P(IB-aze-St)CH2CH2CH2OH](8) stars with 4,4'-methylene bis(phenyl) diisocyanate and 2,4-tolylene diisocyanate in various solvents afforded tightly crosslinked films of potential interest for scratch-resistant coatings, mar-resistant coatings, or both.