Compared with mercury, the existence of [Zn2](2+) species is rare. We succeeded in preparing a stable [Zn2](2+) species by utilizing an MFI-type zeolite as a nano-reaction pot, which was confirmed using XAFS spectroscopy: the bands at R = 2.35 Å due to the Zn(+)-Zn(+) scattering and at 9660.7 eV due to the 1s-σ* (the anti-bonding orbital comprised of the 4s-4s orbital) transition of the [Zn2](2+) species. This species also gives the characteristic band around 42 000 cm(-1) due to its σ-σ* transition. Furthermore, UV-irradiation corresponding to the σ-σ* transition causes the bond dissociation, forming two unprecedented Zn(+) ions, and detached Zn(+) ions were recombined through heat-treatment at 573 K: [Zn(+)-Zn(+)] ⇄ 2Zn(+). These processes were reproduced by applying the DFT calculation method to the assumed triplet, σ(α)-σ*(α), structure formed on the M7-S2 site with the specific Al array in the MFI-type zeolite. Research into the specific field using zeolites to synthesize "ultra-state ions" is very promising.