The invention discloses a free-form surface-based spectral imaging system, which is characterized by comprising an incident slit, a curved prism, a free-form surface reflector, a plane reflector and a detector image plane. The incident slit serves as the object plane of the spectral imaging system. Light rays, far from the heart of an object space, inject onto the curved prism through the incident slit. After the transmission process, the light rays are reflected by the free-form surface reflector, then transmitted through the curved prism again, and finally imaged on the detector image plane after being reflected by the plane reflector. According to the technical scheme of the invention, based on the non-rotation symmetry of the free-form surface, the defect that a grating is low in diffraction efficiency and overlapped in spectral orders can be effectively overcome. Meanwhile, only one reflector and one prism are adopted, so that the aberration caused by the increased field of view can be effectively balanced. The imaging range of the system is enlarged, and the imaging quality of the system is improved. In addition, both the size and the weight of a spectrometer are reduced, and the system is simplified. The system can be applied to airborne applications large in field of view, large in relative aperture and wide in spectrum.