We address the correlation between the crystalline state of photoactive materials in a model organic solar cell based on poly(3-hexylthiophene-2,5-diyl):phenyl-C60-butyric acid methyl ester (P3HT:PCBM) and the photovoltage in an in-operando investigation. I–V curves are simultaneously measured together with grazing incidence wide-angle X-ray scattering probing the crystalline state of the device active layer as a function of the operation time. The results show a high degree of correlation between open-circuit voltage VOC and the crystalline state of P3HT.