Introducing N atoms to the pentacene backbone leads to N-heteropentacenes, whose properties can be tuned by changing the number, position and valence state of N atoms in the pentacene backbone. With a rapid development in recent years, N-heteropentacenes and their derivatives have arisen as a new family of organic semiconductors with high performance in organic thin-fi lm transistors (OTFTs). This article reviews the research efforts of developing N-heteropentacenes into organic semiconductors starting from 2003 with emphasis on the work of the author's group since 2009. The structure-property relationship and design rationale are highlighted based on an overview of reported organic semiconductors of N-heteropentacenes.