Star‐shaped molecules consisting of regioregular poly(3‐hexylthiophene) (P3HT) chains as the arms, attached to either a propeller‐like triphenylamine or a planar triphenylbenzene core, have been synthesized via Suzuki coupling. The structures of the three‐arm star‐shaped poly(3‐hexylthiophene) (s‐P3HT) materials obtained were studied using Fourier transform infrared, 1H and 13C NMR, XRD, gel permeation chromatography and DSC. The s‐P3HT polymers were soluble in common organic solvents and exhibited number‐average molecular weights of 6000–7200 g mol−1. Their optical properties in solutions and in solid state films were investigated using the UV−visible absorption and photoluminescence techniques, and were compared with those of linear P3HT. © 2015 Society of Chemical Industry