The identification of hazardous chemicals based on hyperspectral imaging is an important emergent means for the prevention of explosion accidents and the early warning of secondary hazards. In this study, we used a combination of spectral curve matching based on full-waveform characteristics and spectral matching based on spectral characteristics to identify the hazardous chemicals, and proposed a method to quantitatively characterize the matching degree of the spectral curves of hazardous chemicals. The results showed that the four hazardous chemicals, sulfur, red phosphorus, potassium permanganate, and corn starch had bright colors, distinct spectral curve characteristics, and obvious changes in reflectivity, which were easy to identify. Moreover, the matching degree of their spectral curves was positively correlated with their reflectivity. However, the spectral characteristics of carbon powder, strontium nitrate, wheat starch, and magnesium–aluminum alloy powder were not obvious, with no obvious characteristic peaks or trends of change in reflectivity. Except for the reflectivity and the matching degree of the carbon powder being maintained at a low level, the reflectivity of the remaining three samples was relatively close, so that it was difficult to identify with the spectral curves alone, and color information should be considered for further identification.