Recent advancements in Large Language Models (LLMs) have led to their increasing integration into human life. With the transition from mere tools to human-like assistants, understanding their psychological aspects-such as emotional tendencies and personalities-becomes essential for ensuring their trustworthiness. However, current psychological evaluations of LLMs, often based on human psychological assessments like the BFI, face significant limitations. The results from these approaches often lack reliability and have limited validity when predicting LLM behavior in real-world scenarios. In this work, we introduce a novel evaluation instrument specifically designed for LLMs, called Core Sentiment Inventory (CSI). CSI is a bilingual tool, covering both English and Chinese, that implicitly evaluates models' sentiment tendencies, providing an insightful psychological portrait of LLM across three dimensions: optimism, pessimism, and neutrality. Through extensive experiments, we demonstrate that: 1) CSI effectively captures nuanced emotional patterns, revealing significant variation in LLMs across languages and contexts; 2) Compared to current approaches, CSI significantly improves reliability, yielding more consistent results; and 3) The correlation between CSI scores and the sentiment of LLM's real-world outputs exceeds 0.85, demonstrating its strong validity in predicting LLM behavior. We make CSI public available via: https://github.com/dependentsign/CSI.