High-accuracy wavelength calibration is critical for qualitative and quantitative spectroscopic measurements. Many spectrometers employed in planetary-exploration missions have onboard calibration sources, including standard lamps and calibration targets. However, such calibration sources are not always available because planetary missions, particularly landing missions, usually have limitations in size and mass. Thus, a wavelength calibration method without requiring hardware addition can be highly beneficial. In this study, we demonstrate a method for wavelength calibration using solar Fraunhofer lines observed in the reflectance spectra of planetary surfaces. Using a Raman spectrometer prototype developed for a Phobos rover, we measured the spectrum of the sunlight reflected from a spectral standard, manufactured to provide similar reflectance spectra to the surface of Phobos. We identified 35 Fraunhofer absorption lines in the wavelength range between 530 and 700 nm and utilized these features for the wavelength calibration of the spectrometer. This approach using Fraunhofer lines achieved good results (better than +0.04/−0.06 nm), comparable to the results achieved using a conventional Ne lamp. The wavelength accuracy corresponds to a wavenumber accuracy better than ±1.5 cm−1 in the 0–4000 cm−1 Raman shift (Stokes shift) range with a 532 nm excitation laser. This result enabled the estimation of the magnesium number (Mg#) of olivine, achieving a value more precise than 1.5% based on the Raman peak positions. In addition, we examined the number of solar Fraunhofer lines detectable at different wavelength resolutions by binning the solar spectrum acquired in this study. We found that more than 10 Fraunhofer lines could be detected as prominent absorption lines when the wavelength resolution is higher than 1 nm/pix (30 cm−1/pix at 1000 cm−1). This result suggests that the target-free wavelength-calibration method using solar Fraunhofer lines can be applied to other spectrometers simply by observing sunlit planetary surfaces.