The double crown hexakis[(di-µ-benzylthio) nickel] cluster, [Ni₆(SCH₂C₆H₅)₁₂]·C₂H₅OH, was obtained by reacting C₆H₅CH₂SNa with [(CH₃)₂CHOCS₂]₂Ni in EtOH. The results of electrochemical studies show that [Ni₆(SCH₂C₆H₅)₁₂] is a quasi-reversible process. The crystal structure of [Ni₆(SCH₂C₆H₅)₁₂]·C₂H₅OH is composed of discrete [Ni₆(SCH₂C₆H₅)₁₂] and C₂H₅OH solvent molecules. Each Ni atom is surrounded by four S atoms of the µ₂-SCH₂C₆H₅ ligands in a distorted square-planar structure. The C₆H₅CH₂S^- side chains are arranged in the axial and equatorial positions, alternately, concerning the pseudo-hexagonal axis of the molecule. Strong π-π and C–H···π effects form the supramolecular nano-channel along the a-axis in the crystal, which wraps the solvent ethanol molecules in it. In addition, a wall is formed along the b- and c-axes, so that the ethanol molecules can freely enter and leave along the a-axis. These effects result in the ability of the title compound to adsorb and desorb ethanol molecules. Thermogravimetric analysis and powder X-ray diffraction at different temperature are provided to demonstrate this point.