Recent text-to-SQL systems powered by large language models (LLMs) have demonstrated remarkable performance in translating natural language queries into SQL.However, these systems often struggle with complex database structures and domain-specific queries, as they primarily focus on enhancing logical reasoning and SQL syntax while overlooking the critical need for comprehensive database understanding.To address this limitation, we propose DB-Explore, a novel framework that systematically aligns LLMs with database knowledge through automated exploration and instruction synthesis.DB-Explore constructs database graphs to capture complex relational schemas, leverages GPT-4 to systematically mine structural patterns and semantic knowledge, and synthesizes instructions to distill this knowledge for efficient fine-tuning of LLMs.Our framework enables comprehensive database understanding through diverse sampling strategies and automated instruction generation, bridging the gap between database structures and language models.Experiments conducted on the SPIDER and BIRD benchmarks validate the effectiveness of DB-Explore, achieving an execution accuracy of 67.0% on BIRD and 87.8% on SPIDER. Notably, our open‐source implementation based on Qwen2.5‐Coder‐7B achieves state‐of‐the‐art results at minimal computational cost, outperforming several GPT‐4‐driven Text‐to‐SQL systems.