An orthogonal design was used to optimize the process of making slim medium-density fiberboard modified by a nitrogen-phosphorous series of flame retardants. Mechanical performance was the evaluating criterion. Subsequently, the combustion performances of each type of flame retardant, including in states solid, liquid, and their combination with a ratio of 1:1, were investigated to clarify the corresponding fire-retardant mechanism. The results showed that only physical bonding was responsible for connecting the wood fiber with the retardants, according to the Fourier transform infrared spectrum. Catalytic charring, flame retardancy, and the thermal insulation of three types of retardant were solidified by the results of a cone calorimeter (CONE) analysis, thermogravimetric (TG) analysis, and differential scanning calorimetry (DSC), and the mixture of solid and liquid was demonstrated as the primary choice. It was also found that after the mixture of the solid and liquid retardant was added, the limiting oxygen index of the board reached 43.3%, and it met the requirements of the B1 Class in the Chinese National Standard GB/T8624-2012 (2012).