This Feature Article is aimed at highlighting the recent developments in the transition-metal-free molecular rearrangements involving arynes. The chemistry of arynes has shown incredible developments especially in transition-metal-free carbon-carbon and carbon-heteroatom bond-forming reactions in the last three decades. The rapid growth in this field is mainly due to the development of mild methods for the generation of arynes. One aspect of the recent developments in the chemistry of arynes involves the molecular rearrangements proceeding via this electrophilic intermediate. The molecular rearrangements have provided direct access to a library of valuable molecules, which cannot be accessed in a single step through other synthetic routes. Herein, we present a concise account on the developments that occurred in this field over the last three decades.