A Ce^III linear complex of N-hydroxy-1,8-naphthalenedicarboximide (HL) has been synthesized with acenaphthoquinone dioxime (acndH₂) under solvothermal conditions, in which L is generated by a series of in-situ reactions starting from acndH₂. X-ray crystallography reveals the coordination chains of Ce^III ions are assembled into a 3D supramolecular framework via π···π interactions. The title complex has been characterized by IR and UV-Vis spectra and thermogravimetric analysis (TGA). Furthermore, the fluorescent properties study demonstrated a ligand-based emission of the Ce^III complex with ~6 nm blue-shift compared with the emisision of the HL ligand.