A new class of star-shaped coil-rod diblock copolymer polystyrene-block- poly(3-hexylthiophene) (PS-b-P3HT) with well-defined structures and the ratio of coil to rod blocks were synthesized by a combination of atom transfer radical polymerization, the Grignard metathesis method, and click reaction. The star-shaped PS-b-P3HT diblock copolymers covalently connected to a β-cyclodextrin (β-CD) core were composed of 21-arm coil-like PS inner blocks and rod-like conjugated polymer P3HT outer blocks with narrow molecular weight distribution. The intermediate and final products were systematically characterized and confirmed by gel permeation chromatography (GPC), 1H nuclear magnetic resonance (1H-NMR), and Fourier transfer infrared (FTIR) spectroscopy. The optical properties of star-shaped PS-b-P3HT were examined by UV-Vis absorption and photoluminescence (PL) measurements. In comparison to the linear P3HT, due to their compact structure and the introduction of PS blocks, the optical properties of 21-arm, star-shaped PS-b-P3HT were altered. The star-shaped PS-b-P3HT formed unimolecular micelles in good solvent as revealed by dynamic light scattering (DLS) and atomic force microscopy (AFM) studies.