Smart stimuli‐responsive persistent luminescence materials, combining the various advantages and frontier applications prospects, have gained booming progress in recent years. The trap‐controlled property and energy storage capability to respond to external multi‐stimulations through diverse luminescence pathways make them attractive in emerging multi‐responsive smart platforms. This review aims at the recent advances in trap‐controlled luminescence materials for advanced multi‐stimuli‐responsive smart platforms. The design principles, luminescence mechanisms, and representative stimulations, i.e., thermo‐, photo‐, mechano‐, and X‐rays responsiveness, are comprehensively summarized. Various emerging multi‐responsive hybrid systems containing trap‐controlled luminescence materials are highlighted. Specifically, temperature dependent trapping and de‐trapping performance is discussed, from extreme‐low temperature to ultra‐high temperature conditions. Emerging applications and future perspectives are briefly presented. It is hoped that this review would provide new insights and guidelines for the rational design and performance manipulation of multi‐responsive materials for advanced smart platforms.