This paper introduces a comprehensive performance evaluation algorithm explicitly designed for secondary equipment in substations, specifically targeting the relay protection system. In contrast to the current evaluation systems, this novel method navigates the complex internal interconnections and mechanisms inherent within secondary system equipment. Such complications have previously impeded the accuracy and breadth of evaluations, thereby limiting the degree of precision and innovation attainable within substations. The proposed approach effectively integrates the improved Analytic Hierarchy Process entropy weight (IAHP‐EW) method with the Learning Vector Quantization (LVQ) neural network. Initially, the IAHP‐EW method identified the comprehensive evaluation indicators and their corresponding weights for relay protection devices. Following weight allocation, these evaluation indicators are scrutinized and computed utilizing the multivariate regression analysis algorithm, resulting in performance evaluation outcomes for the relay protection system. These outcomes are subsequently classified and utilized in training the LVQ neural network, promoting the network's capacity to autonomously evaluate the performance status of the relay protection system. To corroborate the viability and effectiveness of this proposed performance evaluation and prediction algorithm, empirical operating data from a local substation is used. The results suggest a significant improvement in the evaluation accuracy of secondary equipment performance, indicating potential for practical application and a valuable contribution to the field through the introduction of a novel approach to performance assessment of substation relay protection systems.