Graft copolymers with a large number of side chains chemically attached onto a linear backbone are endowed with unusual properties thanks to their confined and compact structures, including wormlike conformation, compact molecular dimensions and notable chain end effects. Growing attention has been paid to these interesting macromolecules due to their importance in understanding the correlation between architectures and properties, as well as their potential applications. To date, the synthesis and properties of graft copolymers in both solution and bulk have been extensively investigated, along with their applications. In this tutorial review, recent advances in synthetic approaches towards the construction of well-defined graft copolymers are discussed in detail and applications of these interesting macromolecules are highlighted by selected examples.