Organic semiconductors are becoming increasingly popular due to the ease of solution processeability to obtain devices. To compete with the existing inorganic semiconductors, there are extensive research efforts going on towards improvement of the conductivities in organic conjugated polymeric systems using extrinsic methods. Doping of conjugated polymers with tailored small molecular dopants, referred to as molecular doping, is one of the widely used extrinsic methods to increase the conductivities. Molecular doping leads to oxidation (ptype doping) or reduction (n-type doping) of the host polymer systems via charge transfer processes. The extent of charge transfer along with the strength of interaction between resultant charges are keys to the success of efficient doping process. Thus, a detailed understanding of evolution of electronic interactions during the doping process is paramount.