 Lithium perchlorate monohydrate was synthesized and characterized. The compound crystallizes isotypic to sodium perchlorate monohydrate in the monoclinic space group type C2/c with a = 14.2592(6) Å, b = 5.2921(2) Å, c = 10.3382(4) Å, β = 111.765(2)°, V = 724.52(5) Å3, Z = 8, at T = 110 K. Additionally, we investigated the compound by means of IR and Raman spectroscopy, powder X-ray diffraction, thermal analysis (TG/DSC), and solid-state computational calculations.