In this work, uniform poly(3-methylthiophene) (P3MT) films are fabricated on indium-tin oxide (ITO) surfaces using surface-initiated Kumada catalyst-transfer polycondensation (SI-KCTP) from surface-bound arylnickel(II) bromide initiators. The P3MT interfacial layer is covalently bound to the ITO surface, thereby preventing possible delamination during the processing of additional layers. These surface-bound P3MT layers successfully serve as the hole-transport layer for solution-processed bulk heterojunction polymer solar cells. Efficiencies greater than 5% have been achieved on devices based on doped thin P3MT interfacial layers. Moreover, because of the excellent stability of the covalently immobilized P3MT on ITO substrates, devices based on reused P3MT/ITO substrates extracted from old devices exhibit efficiencies similar to those of the original devices.