A new type epitaxial growth was found in lithium phthalocyanine (LiPc) film on KBr(100) prepared by the molecular‐beam epitaxy. The structure was directly observed by transmission electron microscopy and two epitaxial phases were observed. One is bidirectional tetragonal phase KBr(100)(&sqrt;10×&sqrt;10)R±27°−LiPc. The other is a new type of tetradirectional monoclinic phase (&sqrt;10×&sqrt;12.5), in which LiPc lattices match with both K+and Br−ions, which form unusual unit meshes.