Large Language Models (LLMs) are increasingly deployed in contexts requiring complex moral reasoning and value trade-offs. However, existing evaluations typically rely on item-level behavioral metrics, which fail to capture how models structurally prioritize competing values as a cohesive system. To address this, we propose a symmetric human-LLM evaluation framework, grounded in Q methodology, to measure value-structure alignment. Under our protocol, humans and models sort an identical 140-item moral statement set into a shared nine-column forced distribution; for LLMs, we elicit strict rankings and deterministically map them to Q-sort buckets. Using a human reference sample ($N=35$), we establish a stable three-factor reference geometry specific to this instrument and sample. We evaluate 12 LLMs across four model families via 240 replicated Q-sorts at two temperature settings, quantifying structural alignment via Procrustes similarity ($φ$) and RSA-based Spearman correlation ($ρ$). Our results reveal significant cross-family heterogeneity, model-specific sensitivity to generation stochasticity and localized misalignment, which demonstrate that favorable global scores can obscure underlying regional distortions. While rank- and bucket-based analyses remain highly consistent, prompt phrasing introduces notable variance. Ultimately, assessing value-structure alignment provides a crucial structural complement to traditional itemwise moral benchmarks.

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