The effects of potassium chloride (KCl) on the pyrolysis of medium density fiberboard (MDF) were investigated by using thermogravimetry/Fourier-transfer infrared spectroscopy (TG-FTIR). Five MDF samples treated with different KCl concentrations (0%, 0.5%, 1%, 2% and 3%) were heated with a heating rate of 20 °C/min. The thermogravimetry (TG) results showed that KCl caused the primary pyrolysis stage towards lower temperatures. The FTIR results indicated that with the concentrations of KCl, the formation of CH4 and C=O functional groups decreased while the formation of CO2 and CO increased. To figure out the reason for the observed phenomena, the kinetic parameters in primary pyrolysis and the secondary charring reaction were estimated by a differential evolution (DE) optimization algorithm. The prediction indicated that KCl shifted the initial degradation temperature of each component of MDF towards a lower temperature. Char and gas yields increased with the concentration of KCl, whereas the tar yield reduced. The changes in activation energies revealed that KCl played a catalyst role in the reaction of resin, hemicellulose and cellulose in primary pyrolysis. For lignin, KCl had little effect. In the secondary charring reaction, KCl apparently promoted the reaction of tar. The catalytic effect of KCl on MDF pyrolysis was the combination of primary pyrolysis and the secondary charring reaction. Finally, the optimal catalytic concentration for KCl on MDF pyrolysis was analyzed.