The fabrication of polymer field-effect transistors with good electrical properties requires the minimization of molecular defects caused by low molecular weight (MW) fractions of a conjugated polymer. Here we report that the electrical properties of a narrow bandgap conjugated polymer could be dramatically improved as a result of dipping a thin film into a poor solvent. The dipping time in hexanes was controlled to efficiently eliminate the low molecular weight fractions and concomitantly improve the molecular ordering of the conjugated polymer. The correlation between the structural order and the electrical properties was used to optimize the dipping time and investigate the effects of the low MW fraction on the electrical properties of the resulting thin film.