Recently, the fabrication of ordered luminescent ultrathin film (UTF) materials based on layered double hydroxides (LDHs) has received much attention. However, how to obtain these UTFs assembled by small anions and LDHs nanosheets is still a challenge. Herein, perylene 3,4,9,10-tetracarboxylate (PTCB) was firstly chosen as the anion with the aim to obtain PTCB/LDH UTFs, which cannot be formed based on typical layer-by-layer (LBL) method. Then, the polymer anions (such as poly 4-styrene sulfonate (PSS) and poly vinyl sulfonate (PVS)) were further chosen as the co-assembled units with PTCB, which can act as carriers to assemble with LDH nanosheets. The as-obtained PTCB@PSS/LDH and PTCB@PVS/LDH UTFs present long range ordered structures confirmed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Moreover, these two UTF systems show polarized luminescence with the emissive anisotropy of ca. 0.62 and 0.73. Therefore, this work presents an exfoliation-coassembly way to develop LDH-based ordered luminescent films, which may benefit their future optical display applications.