Multiscale computations were utilized to resolve the detailed solvent polymer interactions in binary (aliphatic/aromatic) solvent media of a standard amphiphilic conjugated polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), revealing an unequivocal pathway specific solvents or hybrid solvents impact the nanomorphology in the eventual quenching state. The significant finding is that, through sophisticatedly compromised, local-phase solvent particle distribution encompassing the polymer chain, certain solvent compositions (i.e., chloroform/chlorobenzene = 2:1 and chloroform/toluene = 1:1 in number density) were noted to bolster exceptional, highly extended chain conformations in solution, which in turn greatly facilitate the incubation of ordered pi-pi stacking upon solvent evacuation via, a relatively-regular chain folding along the pivotal tetrahedral defects. Overall, the simulation helps clarify a long-standing ambiguity as to the molecular effects of specific solvents and, in particular, unveils previously unnoticed physics underlying the promising features of hybrid solvents in casting polymer thin films, as evidenced by recent experiments.