The imperative of global security amidst persistent threats of terrorism, organized crimes, and accidental events underscores the critical role of explosive detection in safeguarding public safety. While effective, traditional detection methods are often time- and resource-intensive and may not always be suitable for on-site applications in specific scenarios. Consequently, there has been a concerted research effort to develop fluorescent materials with diverse sensing mechanisms to achieve heightened sensitivity, selectivity, and rapid response times in explosive detection. This review explores the exploration of supramolecular systems, including cucurbit[n]uril, pillar [n]arenes, cyclodextrin, calixarenes, electron-rich supramolecules, and related complexes, designed to enhance the efficiency of explosive detection. Recent advancements and emerging technologies in this field are discussed in the review, intending to stimulate further inquiry and innovation in synthesizing and applying supramolecular complexes for explosive detection, addressing the urgent demand for heightened security measures.