How to eliminate the thermal history present in differential scanning calorimetry, this question has been widely concerned. Benzil has a serious thermal history that is not well eliminated by conventional thermal history methods. Herein, using benzil as a target, we developed a freeze-gradient temperature rate heating up method to eliminate the thermal history of DSC. Compared with the conventional method, this method avoids the introduction of new thermal histories by new crystalline forms that may appear during the cooling crystallization process. The results show that the peak shape of the melting peak is sharper and the peak emergence position is closer to the theoretical melting point after the elimination of the thermal history by the freeze-gradient heating up method. Based on this method, we optimized other factors to establish a complete method for the determination of melting point by DSC, analyzed the uncertainty of the method, and obtained an extended uncertainty of 0.19°C for DSC in this method. The validation results show that the p-nitrotoluene of the melting point reference substance was 52.64°C, which is within its reference value of (52.53 ± 0.20) °C, showing that this method is reliable. This study provides a reference for other thermal analysis methods to eliminate thermal history.