An issue for the morphology control of organic materials in active layer has still been in spotlight. Most research people have focused on the p-type semiconducting compounds; however, the studies on the n-type materials are rarely conducted. Thus, in this paper, we systematically controlled the morphology of the n-type semiconductor by introducing insulating polymers, PS and PAN. We analyzed the structural variation of the P(NDI2OD-T2):PS and P(NDI2OD-T2):PAN films depending on their blend ratios or thermal annealing treatment. From results, we could understand that the morphology of P(NDI2OD-T2) molecules was varied with random packing orientations. Through our study, we can believe that we suggest a new approach of the morphology control for the n-type semiconducting polymers, which will benefit to other materials.