The chapter introduces and defines the term star-shaped mesogens as a highly symmetric subgroup of multipodes. Hekates, the three arm stars, are in the focus of the other sections. Flexible, semi-flexible and shape-persistent mesogens can be distinguished. The chapter presents various modes of self-assembly which account for nanosegregation and space-filling. Recent examples are semi-flexible structures which fold to E-shaped conformers followed by self-organisation in columnar 2D and 3D and micellar cubic structures. Hekates are mesogens that will allow the design of complex mesomorphic and functional materials in the future.