The dialumane [Al₂][Na(Ph₂pz)₃]₂ (1) has been prepared by the reaction of Na(Ph₂pz) with a metastable solution of AlCl. The structure of 1 contains two hydrotris(pyrazolyl)borate-like Na(Ph₂pz)₃²⁻ moieties that are coordinated to each Al atom of the dialumane in a κ²,κ¹-N,N,N fashion and several π-stacking interactions are present between the pyrazolate and phenyl rings. In solution the pyrazolate ligands in 1 are in dynamic exchange, even at −80 °C, which shows the lability of these ligands to the low-valent aluminum centers.