For the problems that the performance of the nearest neighbor classification algorithm is greatly affected by the adopted similarity or distance measuring method, and it is difficult to select the optimal similarity or distance measuring method, with multi-similarity method adopted, a K-Nearest Neighbor algorithm with Ordered Pairs of Normalized real numbers (OPNs-KNN) was proposed. Firstly, the new mathematical theory of Ordered Pair of Normalized real numbers (OPN) was introduced in machine learning. And all the samples in the training and test sets were converted into OPNs by multiple similarity or distance measuring methods, so that different similarity information was included in each OPN. Then, the improved nearest neighbor algorithm was used to classify the OPNs, so that different similarity or distance measuring methods were able to be mixed and complemented to improve the classification performance. Experimental results show that compared with 6 improved nearest neighbor classification algorithms, such as distance-Weighted K-Nearest-Neighbor rule (WKNN) rule on Iris, seeds, and other datasets, OPNs-KNN has the classification accuracy improved by 0.29 to 15.28 percentage points, which proves that the performance of classification can be improved greatly by the proposed algorithm.