The kinetics of thermal degradation of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) (PEN/PTT) blends with different weight ratio were investigated by thermogravimetry analysis from ambient temperature to 800 °C in flowing nitrogen. The kinetic parameters, including the activation energy Ea, the reaction order n, and the pre-exponential factor ln(Z), of the degradation of the PEN/PTT blends were evaluated by three single heating rate methods and advanced isoconversional method developed by Vyazovkin. The three single heating rate methods used in this work include Friedman, Freeman–Carroll, and Chang method. The effects of the heating rate, the calculation methods, and the content of the PEN component on the thermal stability and degradation kinetic parameters of the PEN/PTT blends were systematically discussed. The PEN/PTT blends which degraded in two distinct stages were stable under nitrogen, also, the maximum rate of weight loss increased linearly with increasing of heating rate and decreased with increasing of PEN content. The obtained kinetics data suggested that the introduction of PEN component increased the activation energy, enhanced the stability of the blend system, and affected the process of degradation of PEN/PTT blend.