Debt collection is a critical negotiation task in the financial industry, with strong practical relevance and exceptional academic value as a behaviorally rich, high-stakes testbed for human-centered dialogue systems. While large language models (LLMs) have shown promise in dialogue and negotiation, effectively evaluating their performance in this complex scenarios remains a major challenge: existing benchmarks uniformly assume users to be static, rational agents with fixed preferences, failing to capture the rich behavioral heterogeneity inherent in real-world debt collection. To bridge this gap, we propose DebtBench, the first public persona-enriched debt collection benchmark, that highlights behavioral heterogeneity in negotiation. Moreover, we develop DebtGPT, a debt collection agent trained to jointly optimize financial recovery and interaction experience. Our experimental results, using 16 state-of-the-art LLMs, find that most existing models struggle in this complex but realistic scenarios, whereas DebtGPT outperforms all open-source baselines and achieves performance on par with GPT-4o. The code and data are available at https://github.com/yyuhhhh13/DebtNegotiation.