Terbium (Tb)-phthalocyanine (pc) sandwich clusters, Tb-n(pc)(n+1) (n = 1-4), and their Na adducts, TbNak(pc)(2) (k = 1-4) were produced by dual laser vaporization of a Tb rod and the molded rod of metal-free or disodium phthalocyanine (H(2)pc/Na(2)pc) in gas phase. The minimum number of Na atoms attached to the cationic/neutral/anionic Tb-1 (pc)(2) clusters is 2, 1, and 0, respectively. Together with the ionization energies of the Na adducts of Tb(Na)(k)(PC)2 (k = 1 and 2), it is revealed that the Tb-pc clusters are formed through fairly ionic bondings, where each component exists as Tb3+, Na+, and pc(2-), respectively.