Single crystals of LiH2PO4 were grown from an aqueous solution by slow evaporation method, the morphology being observed by optical and scanning electron microscopes and the crystal structure being labeled by powder X-ray diffraction. The virtual crystal was simulated in accord with the realistic crystal observed, with the following faces in the space group Pna21−C2v9 : pyramid {111}, {111¯} ; prism {110}; dome {011}, {011¯}, {201¯} ; pedion {001¯}. From comparison of the macroscopic morphology and the microscopic crystal structure, terminating groups of the top layer surfaces are suggested.