Complexation of endohedral metallofullerene La@C-82-A (1) with macrocyclic compounds, such as 1,4,7,10,13,16- hexaazacyclooctadecane (2), 1,4,7,10,13,16- hexamethyl- 1,4,7,10,13,16-hexaazacyclooctadecane (3), mono-aza-18-crown-6 ether 4), 18-crown- 6 ether (5), and p-tert-butylcalix[n] arenes (n) 4-8, 6-10), for the first time is examined. Among them, 1 forms a complex with azacrown ethers 2-4 while accompanying the electron transfer between them. This is characteristic of endohedral metallofullerene and caused by its low reduction potential. Activation energies, Delta Get, for the electron transfer from 2-4 to 1 are 4.6, 2.8, and 11 kcal/ mol, respectively. These small Delta Get values indicate that the electron transfer from the azacrown ethers to 1 is facile in the ground state. Furthermore, the selective isolation of lanthanum endohedral metallofullerenes from the extracts of soot is accomplished by utilizing the complexation of 1 with 2.