Poly(3-hexylthiophene) (P3HT) remains of significant importance as a prototypical benchmark hole conductor material in Organic Photovoltaics (OPVs). In this review we discuss synthetic strategies to P3HT, particularly focusing on those leading to the regioregular form and discussing key physical and morphological properties. Finally, a survey and a brief discussion of P3HT performance in bulk-heterojunction (BHJ) OPVs are also provided.