As AI advances, aligning it with diverse human and societal values grows critical. But how do we define these values and measure AI’s adherence to them? We present ValueCompass, a framework grounded in psychological theories, to assess human-AI alignment. Applying it to five diverse LLMs and 112 humans from seven countries across four scenarios—collaborative writing, education, public sectors, and healthcare—we uncover key misalignments. For example, humans prioritize national security, while LLMs often reject it. Values also shift across contexts, demanding scenario-specific alignment strategies. This work advances AI design by mapping how systems can better reflect societal ethics.