The widespread adoption of Large Language Models (LLMs) has raised significant privacy concerns regarding the exposure of personally identifiable information (PII) in user prompts. To address this challenge, we propose a query-unrelated PII masking strategy and introduce PII-Bench, the first comprehensive evaluation framework for assessing privacy protection systems. PII-Bench comprises 2,842 test samples across 7 PII types with 55 fine-grained subcategories, featuring diverse scenarios from single-subject descriptions to complex multi-party interactions. Each sample is carefully crafted with a user query, context description, and standard answer indicating query-relevant PII. Our empirical evaluation reveals that while current models perform adequately in basic PII detection, they show significant limitations in determining PII query relevance. Even advanced LLMs struggle with this task, particularly in handling complex multi-subject scenarios, indicating substantial room for improvement in achieving intelligent PII masking.