The main objective of this study was to investigate the flame retardant (FR) efficiency of melamine pyrophosphate (MP) with added layered double hydroxide (LDH) in medium density fiberboards (MDFs) to be used as building decorative materials. The thermal degradation, FR efficiency, and combustion properties of MDF were analyzed by Fourier transform infrared spectra (FTIR), thermogravimetric analysis (TGA), limiting oxygen index (LOI) test, and cone calorimetric test. The TGA results showed that the combination of MP and LDH led to a lower decomposition temperature than the pure MP and pure LDH. The LOI results showed that the LOI values increased with the addition of the FRs. The cone calorimetric results showed that the addition of four proportions (1:1, 2:1, 1:2, and 1:3) of the compounds into MDF can clearly decrease the peak heat release rate (PHRR) and mean heat release rate (MHRR). The results indicated that the MP and LDH compounds have a synergistic effect to improve the flame retardancy and smoke suppression in the MDFs. The combination of MP and LDH in a 1:1 ratio under 10 wt% FR addition has the best flame retardant efficiency in the MDFs.