The OFETs showing the best performance are the ones based on blends of PS since they reveal less interfacial traps, leading to devices with higher mobility, threshold voltage close to zero and high bias stress stability. The lowest OFET performance is found in the devices based on PMMA blends due to the higher density of majority charge carrier (i.e., holes) traps. On the other hand, regarding the response of the devices to UV light, the PFS and pristine films exhibited the highest photoresponse, which was attributed to the higher density of minority charge carrier (i.e., electrons) traps. Therefore, this work demonstrates that the binding polymer is a useful tool to optimise the OFET electrical characteristics as well as its photoresponsivity.