With the reform of the education system, the society today raises higher requirements for college teachers, which cause immense psychological stress among them. To enhance the quality of teachers, it is important to analyze the relationship between teaching pressure and self-efficacy. Therefore, this paper tries to analyze and evaluate the relationship between teaching pressure and self-efficacy of college teachers based on artificial neural network. Firstly, a grey correlation analysis (GRA) model was established for the teaching pressure and self-efficacy of college teachers, and the analysis procedure was detailed. Then, the possible multicollinearity of the GRA model was tested. In addition, a linear regression model was established based on Lasso variable selection model and ridge regression variable selection model, aiming to eliminate the multicollinearity between various teaching pressure factors in the GRA model. Finally, a multilabel learning algorithm was proposed based on neural network and label correlation. In this way, the correlations between the various teaching pressure factors and teachers’ self-efficacy were mined automatically. The proposed model proved valid through experiments.