2DES is a nonlinear optical spectroscopic method to study electronic interactions and their dynamics. Unlike conventional 1D spectroscopic study, 2DES provides a correlation between the excitation wavelength (ω τ ) and the probe wavelength (ω t ). This in turn provides information regarding the electronic couplings present between the different electronic states in the system. Our earlier work on PBTTT/F 4 TCNQ has shown the potential of 2DES to study the electronic interactions in molecular doped polymer systems. To capture correlations among the different excitonic states in P3HT/F 4 TCNQ, we recorded 2D electronic photon-echo spectra at room temperature, for various waiting times. We excited the system with a ∼16 fs laser pulse, centered at 13400 cm -1 (760 nm). Laser profile has been such chosen that it covers both, the polaronic band of polymer and the F 4 TCNQ anionic band. Measured 2D spectra (real part) at selected waiting times are shown in Fig. (also see Fig. showing 2D data for additional waiting times). The diagonal peaks in the spectrum correspond to the electronic states excited by the laser and the off diagonal peaks represent the coupling between different electronic states. Diagonal peak, A at ω t = 13000 cm -1 represents a strong ground state bleach feature corresponding to a transition to the higher electronic state of F 4 TCNQ anion ( D 0 → D 1 transition). Another ground state bleach feature, B at ω t = 12380 cm -1 , is present between the two vibronic features of the F 4 TCNQ anions. Similar features were also observed in our previous two-dimensional spectroscopic data on PBTTT, which was calculated to be a PBTTT polaron feature. Thus, we assign here the feature at ω t = 12380 cm -1 to be a signature of P3HT polaron (P2 band). In addition, the off-diagonal peaks C and D at (ω t = 12400, ω τ = 13000) and (ω t = 13250, ω τ = 12250) cm -1 illustrate the presence of coupling in the excitonically coupled electronic states (represented here by peaks A and B) of the P3HT + F 4 TCNQ -ion-pair in chlorobenzene. The excited state absorption feature shown in blue at (ω t = 12500, ω τ = 13750 cm -1 ) possibly represents the D 1 → D n transition. The magnitudes of ground state bleach and excited state absorption features show a dramatic decrease in the later time points, as shown in Fig. ) and (d) corresponding to 2D spectra at 50 and 70 fs, respectively. Thus, 2DES measurements captures the excitonic coupling among the electronic states of the constituent ions of ion-pair in solution and thus, confirm the electronic interaction between the ions. The dynamics of the 2D spectral features can also be used to gain further insight of the system.