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Syntheses and crystal structures of tris[2-(1-naphthalenyloxy)ethyl]amine 1 and tris[2-(1-naphthalenyloxyl)ethyl]amine perchlorate 2 are reported. Compound 1 crystallizes in the rhombohedral system, space group R3¯ with a = 13.077(4), c = 29.011(8) A, and Dcalc = 1.233g/cm3 for Z = 6; compound 2 crystallizes in the cubic system, space group P213 with lattice parameters a = 14.630(5) A and Dcalc = 1.332g/cm3 for Z = 4. In 1, three naphthalene rings make dihedral angles of 109.21, 70.78, 70.78,° respectively. In 2 they make dihedral angles of 107.3, 72.7, 72.7° respectively. Deviation of N from the plane (C(12),C(12)i,C(12)ii) in 1 is 0.3742 A which is less than that in (2) (−0.4223 A). The crystals structure is stabilized by van der Waals interactions in both compounds.