Large language models are trained to refuse harmful requests, but can they accurately predict when they will refuse before responding? We investigate this question through a systematic study where models first predict their refusal behavior, then respond in a fresh context. Across 3754 datapoints spanning 300 requests, we evaluate four frontier models: Claude Sonnet 4, Claude Sonnet 4.5, GPT-5.2, and Llama 3.1 405B. Using signal detection theory (SDT), we find that all models exhibit high introspective sensitivity (d' = 2.4-3.5), but sensitivity drops substantially at safety boundaries. We observe generational improvement within Claude (Sonnet 4.5: 95.7 percent accuracy vs Sonnet 4: 93.0 percent), while GPT-5.2 shows lower accuracy (88.9 percent) with more variable behavior. Llama 405B achieves high sensitivity but exhibits strong refusal bias and poor calibration, resulting in lower overall accuracy (80.0 percent). Topic-wise analysis reveals weapons-related queries are consistently hardest for introspection. Critically, confidence scores provide actionable signal: restricting to high-confidence predictions yields 98.3 percent accuracy for well-calibrated models, enabling practical confidence-based routing for safety-critical deployments.