Abstract: Gas sensors play a pivotal role in the Internet of Things-based environmental monitoring systems, where sensing materials are core determinants of gas sensing performance. However, conventional materials are facing the challenge of realizing complex environment adaptability, high sensitivity and multifunctional compatibility, advanced triboelectric materials show great potential with the advantage of tunable physical and chemical properties. This review aims to summarize the rational design of advanced triboelectric materials with excellent gas-sensitive properties and provide new perspectives for self-powered gas sensing systems. Based on the mechanistic of gas sensing, design strategies for improving the performance of advanced triboelectric materials are illustrated. Additionally, the material’s property modulation and structural design to maintain the stable output of self-powered gas sensing systems are explored. Finally, the emerging applications and future challenges of these materials in gas sensing systems are outlined.