Here we report the first isolation of a series of Yb-containing high metallofullerene based on C-88/C-90/C-92/C-94, along with C-88, C-90 (I, II), C-92, C-94 (I, II) and C-96. Furthermore, the electronic structures of these high fullerenes and metallofullerenes are discussed according to their absorption spectra. It is concluded that for high metallofullerenes, there are usually different isomers with different molecular symmetries while the encaged metal is different, which differs from the case of other small metallofullerenes. In addition, from the discussion of the electronic structural features of the isolated high fullerenes, one can see the special electronic structures of C94S. (c) 2005 Elsevier B.V. All rights reserved.