The portable Raman spectrometer boasts portability, rapid analysis, and high flexibility. It stands as a crucial and powerful technical tool for analyzing the chemical composition of samples, whether biological or non-biological, across diverse fields. To improve the resolution of grating spectrometers and ensure a wide spectral range, many spectrometer systems have been designed with double-grating structures. However, the impact of external forces, such as installation deviations and inevitable collisions, may cause differences between the actual state of the internal spectrometer components and their theoretical values. Therefore, spectrometers must be calibrated to establish the relationship between the wavelength and the pixel positions. The characteristic peaks of commonly used calibration substances are primarily distributed in the 200–2000 cm−1 range. The distribution of characteristic peaks in other wavenumber ranges is sparse, especially for spectrometers with double-channel spectral structures and wide spectral ranges. This uneven distribution of spectral peaks generates significant errors in the polynomial fitting results used to calibrate spectrometers. Therefore, to satisfy the calibration requirements of a dual-channel portable Raman spectrometer with a wide spectral range, this study designed a calibration method based on an optical frequency comb, which generates dense and uniform comb-like spectral signals at equal intervals. The method was verified experimentally and compared to the traditional calibration method of using a mercury–argon lamp. The results showed that the error bandwidth of the calibration results of the proposed method was significantly smaller than that of the mercury–argon lamp method, thus demonstrating a substantial improvement in the calibration accuracy.