In this paper, a novel discriminant methodology based on near infrared spectroscopic analysis technique and least square support vector machine was proposed for rapid and nondestructive discrimination of different types of Polyacrylamide. The diffuse reflectance spectra of samples of Non-ionic Polyacrylamide, Anionic Polyacrylamide and Cationic Polyacrylamide were measured. Then principal component analysis method was applied to reduce the dimension of the spectral data and extract of the principal compnents. The first three principal components were used for cluster analysis of the three different types of Polyacrylamide. Then those principal components were also used as inputs of least square support vector machine model. The optimization of the parameters and the number of principal components used as inputs of least square support vector machine model was performed through cross validation based on grid search. 60 samples of each type of Polyacrylamide were collected. Thus a total of 180 samples were obtained. 135 samples, 45 samples for each type of Polyacrylamide, were randomly split into a training set to build calibration model and the rest 45 samples were used as test set to evaluate the performance of the developed model. In addition, 5 Cationic Polyacrylamide samples and 5 Anionic Polyacrylamide samples adulterated with different proportion of Non-ionic Polyacrylamide were also prepared to show the feasibilty of the proposed method to discriminate the adulterated Polyacrylamide samples. The prediction error threshold for each type of Polyacrylamide was determined by F statistical significance test method based on the prediction error of the training set of corresponding type of Polyacrylamide in cross validation. The discrimination accuracy of the built model was 100% for prediction of the test set. The prediction of the model for the 10 mixing samples was also presented, and all mixing samples were accurately discriminated as adulterated samples. The overall results demonstrate that the discrimination method proposed in the present paper can rapidly and nondestructively discriminate the different types of Polyacrylamide and the adulterated Polyacrylamide samples, and offered a new approach to discriminate the types of Polyacrylamide.