The donor/acceptor inter-mixing in bulk heterojunction (BHJ) solar cells is a critical parameter, often leading to irreproducible performance of the finished device. An alternative solution-processed device fabrication strategy towards a better control of the micro/nano-structured morphology consists of a sequential coating of the donor (e.g., poly-(3-hexylthiophene), P3HT) and the acceptor (e.g., [6,6]-phenyl-C61-butyric acid methyl ester, PCBM) from orthogonal solvents. We demonstrate that, in spite of the solvent orthogonality, this technique does not lead to a well-defined bilayer with a sharp interface, but it rather results in a graded vertical phase-separated junction, resulting from the diffusion of the PCBM in the P3HT bottom layer. We are able to control the diffusion of PCBM, which occurs preferentially in the amorphous P3HT domains, by easily varying the ratio between crystalline/amorphous domains in the P3HT. Such a ratio can be simply modified by changing the solvent for P3HT. We show that the donor–acceptor diffused bilayer (DB) junction is an intermediate structure which combines both advantages of the well-defined bilayer and conventional BHJ configurations. Indeed, the DB device geometry ensures the good reproducibility and charge percolation, like the well-defined bilayer, while preserving the interpenetration of the donor and acceptor species, resulting in an efficient charge separation, characteristic of the BHJ. Overall the annealed DB device geometry can be assimilated to a graded BHJ with an improved reproducibility and mean power conversion efficiency (PCE) of 3.45%, higher than that of the standard BHJ devices of 3.07%. Furthermore, we demonstrate the highest performance for the as-cast DB device with a PCE of 2.58%. It is worthy to note that our DB device exhibits improved open circuit voltage, fill factor, series and shunt resistances, which denote that the vertically phase separated DB junction ensures improved charge percolation.