A series of polypyrazolylaluminates [Na{Al(tBu2pz)4−xMex}] (x = 3 (1); x = 2 (2); x = 1 (3)) were prepared by treatment of [Na(tBu2pz)] with varying equivalents of AlMe3. The reaction of [Na(tBu2pz)] with 1 equiv of AlMe3 afforded the monopyrazolylaluminate [{Na{Al(tBu2pz)Me3}}3(THF)2]∞ (1) as a colorless crystalline solid in 85% yield. Addition of 1 and 2 equiv of tBu2pzH to prepared in situ complex 1 in THF/toluene solutions afforded the bis- and trispyrazolylaluminates Na{Al(tBu2pz)2Me2}(THF)]2 (2) and [Na{Al(tBu2pz)3Me}(THF)] (3) in 81% and 80% yield, respectively, as colorless crystalline solids. Characterization of 1−3 was accomplished by microanalysis and spectroscopic methods as well as single-crystal X-ray crystallography. Crystal structures for 1−3 revealed polymeric, dimeric, and monomeric structures, respectively; for 1 and 2, the aggregation of the complexes is the result of Al−Me···Na bridges and the variety of coordination modes displayed by the pyrazolyl moieties. In a different approach to obtain 3, complex [Me2Al(tBu2pz)2Na(tBu2pzH)] (4) was isolated from a reaction of [(η1:η1-tBu2pz)(μ-AlMe2)]2 with 2 equiv of tBupzH and tBu2pzNa. The molecular structure of 4 shows an Al−Me···Na interaction that activates the bridging methyl group to produce unsolvated 3 in solution at room temperature. Complex 4 may be considered a reaction intermediate that affords complex 3 from 2 and constitutes the first example of the isolation of an intermediate in the synthesis of a ligand analogous to the polypyrazolylborates.