Organic/polymeric semiconductors are mainly composed of aromatic systems including phenyl, vinyl, alkynyl, thienyl, and other isoelectric groups, which are constructed of carbon, hydrogen, and so-called 'hereroatoms' including chalcogen, nitrogen, and halogen atoms etc. The introduction of heteroatoms could yield different electronic properties by influencing the molecular geometry, the HOMO and LUMO energy levels, intermolecular interactions and so on. In this Research News article, we provide a brief review of the effect of heteroatoms and recent developments in heteroatom substituted organic/polymeric semiconductors, focusing especially on their application in field-effect transistors.