For organic photovoltaic devices (OPVDs), controlling the molecular orientation is crucial for obtaining high efficiency. In the present research, highly oriented crystalline films of thiophene-phenylene co-oligomer (TPCO) material were grown on a thin orientation template of friction-transferred polythiophene (PT). To further increase the orientation, thermal treatments were performed to induce recrystallisation of the TPCO layer. XRD, SEM, and polarised absorption analyses confirmed a high level of orientation, demonstrating that the annealing could further enhance the orientation. Moreover, the annealed samples exhibited a promising block-like crystal structure, which has the potential for creating an interpenetrated bulk heterojunction. Based on this structure, OPVDs were fabricated having TPCO molecules and C70 as the organic semiconductors, and, subsequently, their electrical properties were evaluated.