Biogenic amines are a group of nitrogen substances and widely adopted to assess the food safety, especially for the aquatic products. In China, crayfish (Prokaryophyllus clarkii) have become one of the most famous aquatic products and form a complete industrial value chain. To ensure the safety of the crayfish industrial chain, a rapid and nondestructive method for determining the biogenic amines of crayfish by nearinfrared spectroscopy coupled with chemometrics was proposed in this study. The quantitative models of histamine, tyramine, cadaverine, and putrescine were built by using the partial least squares (PLS) regression. The spectral preprocessing and the wavelength selection methods were adopted to optimize the models. For histamine, cadaverine, and putrescine in peeled or whole tails, reasonable quantitative results can be obtained by using the optimized models; the coefficient of determination (r²) are 0.88 and 0.90, 0.88 and 0.91, 0.89, and 0.84, respectively. As for tyramine in peeled or whole tails, the results are acceptable and the coefficient of determination (r²) is 0.83 and 0.74, respectively.