Identification of plant species and variety has important application value in the process of agricultural production. In this work, we try to use electrochemical fingerprinting technology to collect the electrochemical behavior of electrochemically active substances in plant leaf tissues. Twenty Lycium species and varieties were specifically selected to investigate the recognition ability of electrochemical fingerprinting. Two different extraction solvents and electrolytes were used to create different collection environments. The results show that different Lycium spp. can exhibit different electrochemical fingerprints. Different species of the same species exhibit relatively similar electrochemical fingerprints. After the second derivative processing, the electrochemical fingerprint of plants can be used for classification and recognition by different machine learning models. Partial least squares discriminant analysis (PLS-DA), k-nearest neighbor, (KNN), support vector machine (SVM), random forest (RF) and stochastic gradient boosting (SGB) were used to establish recognition model of Lycium spp. The results show that SGB has the best identification accuracy for electrochemical fingerprint after second derivative treatment.