The molecular order and vertical component distribution are critical to enhance the charge transport in layer-by-layer (LbL) processed active layer. However, the excessive inter-diffusion between donor and acceptor layers during LbL processing irrepressibly reduces their ordered packing. Herein, a novel tactic to optimize the molecular order and vertical morphology of the active layer through suppressing the deep penetration of (5Z,5 & PRIME;Z)-5,5 & PRIME;-((7,7 & PRIME;-(4,4,9,9-tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6 -b & PRIME;]dithiophene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole-7,4-diyl))bis(methanylylidene)) bis(3-ethyl-2-thioxothiazolidin-4-one) (O-IDTBR) to poly(3-hexylthiophene) (P3HT) film during LbL processing is proposed. This is enabled by inducing the formation of P3HT nanofibers through ultraviolet (UV) irradiation and solution aging. During the LbL processing, these nanofibers with high crystallinity reduce the damage of O-IDTBR solution to P3HT film and restrict the penetration of O-IDTBR into P3HT matrix. As a result, the P3HT nanofibers are preserved and the degree of vertical phase separation is enlarged in the LbL-processed film. Meanwhile, the molecular order of both components is enhanced. The resulting morphology that featured as intertwined P3HT nanofibers/O-IDTBR network efficiently promotes charge transport and extraction, boosting the power conversion efficiency (PCE) of the devices from 6.70 & PLUSMN; 0.12% to 7.71 & PLUSMN; 0.10%.