As an important kind of material with a layered structure, NiFe-LDHs have been applied extensively in many fields due to their outstanding properties. However, the severe aggregation behavior between nanoparticles greatly limits the application performance of such materials. Herein, we propose a facile and efficient approach for preparing well-dispersed NiFe-LDH nanoparticles with excellent UV-blocking properties. First, NiFe-LDH nanoparticles with an average particle size of 44 nm were successfully synthesized via a coprecipitation method combined with the in situ surface modification technique. After that, highly crystalline materials consisting of NiFe-LDH-heated nanoparticles were achieved with hydrothermal treatment at 120 °C or a higher temperature. It is worth noting that the particle size increased with the increasing temperature, and the morphology of particles turned into hexagonal nanoflakes gradually. Based on the as-obtained NiFe-LDH-heated nanoparticles, highly transparent and flexible PVA-LDH nanocomposite films were readily fabricated. According to the characterizations, these as-prepared nanocomposite films exhibited splendid performance on optical transparency, UV-blocking, and mechanical properties when the filling amount of NiFe-LDH-heated nanoparticles was increased to 20% or higher. In particular, the methylene blue (MB) solution showed a much slower degradation rate under the radiation of UV light with the protection of a NiFe-LDH-heated nanocomposite film compared with the samples protected with a pure PVA film or without any blocking, which demonstrated the distinguished UV-blocking ability of these as-prepared NiFe-LDH-heated nanoparticles. It is expected that this green approach is prospective for the large-scale preparation of NiFe-LDH nanomaterials with excellent UV-blocking performance and some other properties.