This work reports the selective reduction of a number of small molecules by a Zn(I) − Zn(I)-bonded compound. Reaction of dizinc compound [L2Zn2] [L = CH3C(2,6-iPr2C6H3N)CHC(CH3)(NCH2CH2PPh2)] with white phosphorus generated a trimetallic cluster [(LZn)3(μ, κ2: κ2: κ1-P7)], which contained a zinc-coordinated Zintl ion [P7]3−. The low valent Zn(I) compound [L2Zn2] could also reduce 1-azidoadamantane and diphenyl disulfide to selectively afford Zn(II) hexazene complex [L2Zn2(μ-1,6-Ad2-N6)] and thiolate derivative [LZnSPh], respectively. In contrast, oxidation reaction selectively occurred at the pendant phosphine of ligand backbone when reacting [L2Zn2] with elemental sulfur, whereas Zn(I) − Zn(I) bond remained intact.