A simplified approach towards the synthesis of high molecular weight (Mw > 50 kg mol−1) poly(3-hexylthiophene) (P3HT)-based all-conjugated block copolymers is demonstrated and applied to prepare a series of all-conjugated block copolymers. Grazing-incidence X-ray scattering measurements show that P3HT crystallization is suppressed in all-conjugated block copolymers with low (<25 wt%) P3HT content.