To study the electronic interactions in precursor solution mixture of P3HT/F 4 TCNQ, we have used a combination of two-dimensional electronic spectroscopy (2DES) measurements along with the molecular dynamics (MD) simulations of solution mixture. The 2DES measurements capture the electronic interactions amongst the ion-pair in chlorobenzene via off-diagonal coupling between the polymer cation and F 4 TCNQ anion electronic transitions. We used the observed excited state dynamics of the F 4 TCNQ anion to postulate the presence of different types of electronic interaction between ion-pairs in solution, which is further supported by our MD simulations. Analysis of the MD trajectories provide possible interaction modes operational in precursor solution mixtures. We further complement our findings with electronic structure calculations, which reveal the excitonic coupling strengths amongst different mode geometries, and thus provide the much needed detailed understanding of the possible seed structures in precursor solution mixtures.