Ultra-reliable and low-latency communication (URLLC) will play a key role in fifth-generation (5G) and beyond networks, enabling mission-critical applications. Meeting the stringent URLLC requirements, characterized by extremely low packet error rates and minimal latency, calls for advanced statistical modeling to accurately capture rare events in wireless channels. Traditional methods, such as those that rely on large datasets and computationally intensive estimation techniques, often fail in real-time scenarios. In this paper, a novel framework is proposed to meet URLLC requirements through a synergistic integration of extreme value theory (EVT) with generative artificial intelligence (AI). EVT is used to model channel tail distributions, providing an accurate characterization of rare events. Concurrently, generative AI enables data augmentation and channel parameter estimation from limited samples. The integration of EVT with generative AI can thus help overcome the limitations of generative models in capturing extreme events during channel characterization. Using an experimental dataset collected from an automotive environment, it is demonstrated that this integration enhances data augmentation for extreme quantiles, while requiring fewer samples than traditional analytical EVT methods and generative baselines in online estimation of channel distribution.