Abstract: To address challenges in intelligent substation process-layer networked relay protection—including uncertain sampling value transmission delays, difficulties in multi-interval data synchronization, and susceptibility of cross-interval protection coordination to communication anomalies—this paper proposes a protection technology combining time-aware shaping and distributed agent collaboration. The study establishes a stochastic network calculus model for sampling value packets, quantifies the impact of queue delays and burst traffic on synchronization accuracy, and develops a distributed protection agent coordination framework based on a publish/subscribe architecture. A Markov chain-based link monitoring and evaluation model is introduced to dynamically adjust collaborative timeout thresholds. Experimental results demonstrate that the proposed technology maintains output time differences between interval action criteria within 1.0 ms and ensures collaborative tripping dispersion does not exceed 0.5 ms, effectively guaranteeing real-time sampling value transmission and reliable coordinated actions that meet the high-speed response and high-tripping reliability requirements of grid-based relay protection systems.