Charge separation and recombination are key processes determining the performance of organic optoelectronic devices. Here we combine photoluminescence and photovoltaic characterisation of organic solar cell devices with ultrafast multi-pulse photocurrent spectroscopy to investigate charge generation mechanisms in the organic photovoltaic devices based on a blend of an alternating polyquinoxaline copolymer with fullerene. The combined use of these techniques enables the determination of the contributions of geminate and bimolecular processes to the solar cell performance. We observe that charge separation is not a temperature-activated process in the studied materials. At the same time, the generation of free charges shows a clear external-field and morphology dependence. This indicates that the critical step of charge separation involves the non-equilibrium state that is formed at early times after photoexcitation, when the polaronic localisation is not yet complete. This work reveals new aspects of molecular level charge dynamics in the organic light-conversion systems.