Odor dominates more in the quality inspection of traditional Chinese herbal medicines. This paper focuses on what’s effect the electronic nose technology has played if applied in biopharmaceutical test based on odor diagnosis. There are some methods such as literature and data analysis, tests that are used for study. On the basis of brief introduction to the electronic nose technology, the electronic nose PEN3 acquires the overall information of the volatile odor from the miscible Chinese herbal medicines of three typical families. The eigenvalues extracted by the Principal Component Analysis (PCA) act as the input values for mode recognition method to test the three groups of miscible medicine materials. The results reveal that only the Amomum villosum in the training set samples is misjudged, the correct rate reaches 93.23%, and the rest are all 100%. It is suggested that the electronic nose technology can realize the test on miscible Chinese herbal medicines, thus providing a new idea for testing the biopharmaceuticals.