Photocrosslinkable bromine-functionalized poly(3-hexylthiophene) (P3HT-Br) copolymers designed for application in solution-processed organic photovoltaics are prepared by copolymerization of 2-bromo-3-(6-bromohexyl) thiophene and 2-bromo-3-hexylthiophene. The monomer ratio is carefully controlled to achieve a UV photocrosslinkable layer while retaining the π–π stacking feature of the conjugated polymers. The new materials are used as electron donors in both bulk heterojunction (BHJ) and bilayer type photovoltaic devices. Unlike devices prepared from either P3HT:PCBM blend or P3HT-Br:PCBM blend without UV treatment, photocrosslinked P3HT-Br:PCBM devices are stable even when annealed for two days at the elevated temperature of 150 °C as the nanophase separated morphology of the bulk heterojunction is stabilized as confirmed by optical microscopy and grazing incidence wide angle X-ray scattering (GIWAXS). When applied to solution-processed bilayer devices, the photocrosslinkable materials show high power conversion efficiencies (∼2%) and excellent thermal stability (3 days at 150 °C). Such performance, one of the highest obtained for a bilayer device fabricated by solution processing, is achieved as crosslinking does not disturb the π–π stacking of the polymer as confirmed by GIWAXS measurements. These novel photocrosslinkable materials provide ready access to efficient bilayer devices thus enabling the fundamental study of photophysical characteristics, charge generation, and transport across a well-defined interface.