arXiv:2507.15393v1 Announce Type: cross Abstract: Phishing emails are a critical component of the cybercrime kill chain due to their wide reach and low cost. Their ever-evolving nature renders traditional rule-based and feature-engineered detectors ineffective in the ongoing arms race between attackers and defenders. The rise of large language models (LLMs) further exacerbates the threat, enabling attackers to craft highly convincing phishing emails at minimal cost. This work demonstrates that LLMs can generate psychologically persuasive phishing emails tailored to victim profiles, successfully bypassing nearly all commercial and academic detectors. To defend against such threats, we propose PiMRef, the first reference-based phishing email detector that leverages knowledge-based invariants. Our core insight is that persuasive phishing emails often contain disprovable identity claims, which contradict real-world facts. PiMRef reframes phishing detection as an identity fact-checking task. Given an email, PiMRef (i) extracts the sender's claimed identity, (ii) verifies the legitimacy of the sender's domain against a predefined knowledge base, and (iii) detects call-to-action prompts that push user engagement. Contradictory claims are flagged as phishing indicators and serve as human-understandable explanations. Compared to existing methods such as D-Fence, HelpHed, and ChatSpamDetector, PiMRef boosts precision by 8.8% with no loss in recall on standard benchmarks like Nazario and PhishPot. In a real-world evaluation of 10,183 emails across five university accounts over three years, PiMRef achieved 92.1% precision, 87.9% recall, and a median runtime of 0.05s, outperforming the state-of-the-art in both effectiveness and efficiency.