High area-to-mass ratio space debris currently poses an increasing hazard to active satellites in orbit and manned space activities. Due to the difficulties in recognition and cataloging of high area-to-mass space debris, a method based on spectroscopic observations is proposed. This method corrects atmospheric extinction and the impact of telescope optical system on the basis of image preprocessing, extracts space debris reflectance spectroscopy, then compares with the spectral curves of sample materials and recognizes surface materials of high area-to-mass ratio space debris. Results of spectroscopic observations show that it will be fairly accurate if high area-to-mass ratio space debris is composed of a single material, such as aluminum and white paint, and the correlation coefficients of aluminum and white paint are approximately 0.9.