A thermally crosslinkable poly(cyclopentadithiophene-alt-benzothiadiazole) (PCPDTBT) analogue copolymer with 2-ethylhexyl group and 5-hexenyl group on 4,4-positions of cyclopentadithiophene has been synthesised by palladium catalyzed Suzuki coupling reaction. Space-Charge Limited Current (SCLC) devices show hole mobility of up to 3 × 10−4 cm2 V−1 s−1. In addition, organic photovoltaics (OPVs) were fabricated using fullerene derivatives as acceptor materials. The best performing device exhibited Power Conversion Efficiency (PCE) at 2.0%, which could be improved to 3.7% after inclusion of dithiol additives. Most significantly, the lifetime of the OPV was enhanced by the crosslinking; when light soaked at 1 sun of irradiance, a half-life, t1/2 = 419 hours was measured, which is 51% improvement over an OPV using standard PCPDTBT. This higher stability is accounted for the crosslinkable structure of the polymer after annealing. The crosslinking reaction was confirmed by solubility tests, Fourier transform infrared spectroscopy and morphological analysis conducted by Atomic Force Microscopy and simultaneous synchrotron grazing-incidence small-/wide-angle X-ray scattering.