The unreacted equation of state (EOS) for an unreacted explosive can provide fundamental information to understand any analytical model for the shock and initiation process. Based on the Hugoniot expression in Jones–Wilkins–Lee (JWL) form derived from the Mie–Grüneisen EOS and conservation equation across the shock wave, a three-point calibrating method to determine the JWL EOS parameters for unreacted explosives was developed using intelligent algorithms and shock Hugoniot relationship of the explosives considered. The calibration method proposed utilizes the back propagation neural network to predict the nonlinear system composed of different JWL parameter sets; the genetic algorithm is then used to find the optimal solution of the JWL parameter set. Unreacted JWL EOS parameters of eight typical explosives were calibrated using the calibrating method developed, and an excellent agreement can be observed between JWL EOS and experimental p–v curves for all eight explosives selected, indicating the high accuracy of the three-point calibrating method. However, the effectiveness of the three-point calibrating method was experimentally validated with the experimental data measured from the shock tests of the dihydroxylammonium 5,5′-bitetrazole-1,1′-dioxide (TKX-50)-based explosive, where the JWL p–v curve derived from the three-point calibrating method is in good agreement with the experimental curve.