<p indent="0mm">Non-benzenoid polycyclic aromatic hydrocarbons (PAHs) have unique physicochemical properties that are different from benzenoid PAHs. Non-benzenoid PAHs containing seven-membered carbon rings have attracted much attention from synthetic chemists in the past decades and have been used as new building blocks in organic optoelectronic materials. In this review, we summarized and discussed the recent progress in this field, including the new synthetic methods for constructing seven-membered carbon rings in non-benzenoid PAHs reported in recent years, and the applications of these conjugated molecules in organic semiconductors, chiral optical materials and magnetic materials.