Evaluating Large Language Models (LLMs) for mental health support poses unique challenges to reliable evaluation due to the emotionally and cognitively complex nature of therapeutic dialogue. Existing benchmarks are limited in scale, authenticity, and reliability, often relying on synthetic or social media data, and lack frameworks to assess when automated judges can be trusted. To address the need for large-scale authentic dialogue datasets and judge-reliability assessment, we introduce two benchmarks that provide a framework for generation and evaluation in this domain. MentalBench-100k consolidates 10,000 authentic single-session therapeutic conversations from three real-world scenarios datasets, each paired with nine LLM-generated responses, yielding 100,000 response pairs. MentalAlign-70k reframes evaluation by comparing four high-performing LLM judges with human experts across 70,000 ratings on seven attributes, grouped into Cognitive Support Score (CSS) and Affective Resonance Score (ARS). We then employ the Affective–Cognitive Agreement Framework, a statistical methodology using intraclass correlation coefficients (ICC) with confidence intervals to quantify agreement, consistency, and bias between LLM judges and human experts. Our analysis reveals systematic inflation by LLM judges, strong reliability for cognitive attributes such as guidance and informativeness, reduced precision for empathy, and some unreliability in safety and relevance. Our contributions establish new methodological and empirical foundations for the reliable and large-scale evaluation of LLMs in mental health contexts.