The effect of impurities on the optoelectronic and charge transport properties of semiconducting polymers was investigated through the performance of organic photovoltaics (OPVs) and organic field effect transistors (OFETs), respectively. A model representative semiconducting polymer, i.e., poly(3-hexylthiophene) (P3HT), was synthesized and purified using different methods such as precipitation, metals' complexation, and Soxhlet extraction. After the purification processes, each fraction was analyzed to determine its composition in metals (impurities) by various techniques. OFETs and OPVs fabricated from these purified polymer fractions were found to show different charge carrier properties and photovoltaic behaviors. The purest fraction which was obtained after Soxhlet extraction complemented by metals' complexation with the help of ethylenediamine and 15-crown-5 ether showed the best performance in both OPVs and OFETs.