Two new Cu^II complexes, (CuL¹N₃)ClO₄ (1) and (CuL²N₃)ClO₄ (2), have been synthesized and characterized in the presence of NaN₃, where L¹ = tris[2-(6-methylpyridyl)methyl]amine and L² = tris[(3,5-dimethylpyrazol-l-yl)methyl]amine, and their crystal structures have been determined by X-ray diffraction methods. Compound 1 crystallizes in the triclinic space group P–1, with a = 8.258(2) Å, b = 11.481(2) Å, c = 14.158(3) Å, = 72.30(3)°, = 79.05(3)°, = 86.08(3)°, V = 1255.4(5) ų. Compound 2 crystallizes in the monoclinic space group C2/c, with a = 26.752(2) Å, b = 10.561(2) Å, c = 21.059(4) Å, = 120.51(3)°, V = 5126(3) ų. In both compounds, each Cu^II center is in a distorted trigonal–bipyramidal coordinated environment with four nitrogen atoms from the tripodal ligand and one nitrogen atom from the azide group. The coordination geometry around Cu^II center of 1 is axially compressed trigonal bipyramid, while that of 2 is an axially elongated trigonal bipyramid. The coordinated azide group is in the axial site in both complexes. A quasi-dimeric structure of 1 has been formed in the unit cell through hydrogen bonding. The electronic spectra of two complexes in solution have been further studied by UV–vis technique, and the coordination properties have been discussed.