The combination of two or more seemingly distinct properties into a unique composite is an exciting direction for the fabrication of novel multifunctional materials. A vacuum-filtration method was used to fabricate strong and multifunctional heparin/layered double hydroxide (HEP/LDH) films mimicking nacre. The experimental results confirm that the prepared films show a layered nano/microscale-hierarchical structure, in which the LDHs are aligned, with a very high loading amount of LDHs closely comparable to that in the natural nacre, up to 87.5 wt %. Both the modulus (Er ≈ 23.4 GPa) and hardness (H ≈ 0.27 GPa) of the HEP/LDH films are remarkably high. Furthermore, the hybrid films show a combination of outstanding properties of UV-blocking and fire-resistance properties. Therefore, this work provides a way of fabricating multifunctional organic–inorganic hybrid films, which have potential applications in the areas of optical applications, transportation, and construction.