Accurate evaluation of rice storage quality is a core prerequisite for ensuring national food security and industrial benefits. However, traditional physicochemical tests, with their long detection cycles, cumbersome operations, and destructiveness, have become insufficient to meet the urgent needs of rapid and non-destructive evaluation in the modern grain storage, transportation, and processing fields. As sensitive molecular probes reflecting quality deterioration during storage, dynamic changes in volatile organic compounds (VOCs) provide a new approach to breaking through this bottleneck. This paper aims to systematically elaborate on the biochemical sources and categories of VOCs in rice, review the mainstream analytical techniques and data interpretation strategies, and give an in-depth analysis of the key challenges faced by current research and future development directions, in order to provide a theoretical basis and forward-looking guidance for constructing a scientific and efficient evaluation system for rice storage quality.