The invention relates to a crystal form A of 5-methyl-(6S)-tetrahydrofolic acid and a preparation method thereof. The crystal form A of the 5-methyl-(6S)-tetrahydrofolic acid has characteristic peaks at about 7.3, 9.3, 11.6, 12.1, 14.0, 14.4, 15.6, 16.7, 17.2, 18.2, 18.5, 18.9, 19.9, 20.8, 21.5, 21.8, 22.1, 22.6, 23.2, 23.5, 23.9, 24.4, 24.7, 25.6, 26.5, 27.1, 27.8, 28.4 and 29.1 in X-ray powder diffraction expressed by 2[theta] by utilization of Cu-K[alpha] radiation. The crystal form A of the 5-methyl-(6S)-tetrahydrofolic acid is good in stability, high in purity, good in reproducibility and good in dissolvability. The preparation method is simple and is suitable for industrial production.