The invention discloses two novel crystal forms of 9-nitrocamptothecin and preparation methods thereof. In the X-ray powder diffraction pattern with copper target as a radiation source, the crystal form I has characteristic diffraction peaks at the diffraction angle 2theta of 5.8+ / -0.1 degrees, 7.4+ / -0.1 degrees, 8.8+ / -0.1 degrees, 10.5+ / -0.1 degrees, 11.3+ / -0.2 degrees, 11.7+ / -0 degrees, 15.7+ / -0.2 degrees, 17.8+ / -0.1 degrees, 18.7+ / -0.1 degrees, 21.1+ / -0.1 degrees, 24.1+ / -0.1 degrees and 26.2+ / -0.1 degrees and the crystal form II has the characteristic diffraction peaks at the diffraction angle 2theta is 6.1+ / -0.2 degrees, 6.7+ / -0.1 degrees, 7.5+ / -0.2 degrees, 9.4+ / -0.1 degrees, 11.4+ / -0.2 degrees, 12.4+ / -0.1 degrees, 14.1+ / -0.1 degrees, 15.1+ / -0.1 degrees, 17.6+ / -0.1 degrees, 19.7+ / -0.1 degrees, 22.6+ / -0.1 degrees, 23.8+ / -0.1 degrees, 25.2+ / -0.1 degrees, 27.3+ / -0.1 degrees and 29.2+ / -0.2 degrees. The preparation methods of the two novel crystal forms of 9-nitrocamptothecin are based on a supercritical anti-solvent process. The solubility of the prepared novel crystal forms I and II of 9-nitrocamptothecin is higher than that of the existing crystal forms of 9-nitrocamptothecin, and the thermal stability of the prepared novel crystal forms I and II of 9-nitrocamptothecin is more excellent than that of the existing crystal forms of 9-nitrocamptothecin.