We report the preparation of single-layer layered double hydroxide (LDH) two-dimensional (2D) nanosheets by exfoliation of highly crystalline NiAl-NO3 LDH. Next, these unilamellar moieties have been incorporated layer-by-layer (LbL) into a poly(sodium 4-styrenesulfonate)/LDH nanosheet multilayer ultrathin film (UTF). Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible light (UV-vis), and X-ray diffraction (XRD) profiles have been used to follow the uniform growth of the UTF. The use of a magnetic LDH as the cationic component of the multilayered architecture enables study of the resulting magnetic properties of the UTFs. Our magnetic data show the appearance of spontaneous magnetization at ∼5 K, thus confirming the effective transfer of the magnetic properties of the bulk LDH to the self-assembled film that displays glassy-like ferromagnetic behavior. The high number of bilayers accessible-more than 80-opens the door for the preparation of more-complex hybrid multifunctional materials that combine magnetism with the physical properties provided by other exfoliable layered inorganic hosts.