Due to inclusion function and easy chemical modification of calixarenes, they should be able to form inclusion complexes with free radicals, spin labeled calixarenes, and polyradicals based on calixarene skeletons. It is therefore important not only to utilize radicals as spin probes to investigate inclusion function and conformational changes of calixarenes, but also to develop potentially new molecular magnetic devices and materials. Recent research advances, especially using ESR technique, in interdiscipline of calixarene and radical, are briefly reviewed.