This paper explores the combination of a data mining-based state evaluation method for electrical equipment in substations, analyzing the effectiveness and accuracy. First, a Gaussian mixture model is applied to fit all raw data of electrical equipment. The Expectation Maximization algorithm summarizes the data distribution characteristics and identifies outliers. The a priori algorithm is then employed for data mining to derive frequent itemsets and association rules between equipment quality and measurement data. For new equipment samples, conditional probabilities of each feature are independently calculated and combined to classify and evaluate equipment quality. The results suggest that equipment reliability in smart substations can be inferred from historical and real-time operational data using improved association rule algorithms and Naive Bayes classifiers. Finally, the proposed method was applied to analyze statistical data from a 110 kV substation of a power supply company. The states prediction accuracy exceeded 95% when compared with actual equipment quality. The effectiveness evaluation metrics demonstrated that this method outperforms single-category algorithms in terms of accuracy and discrimination ability.