Human cognition significantly influences expressed behavior and is intrinsically tied to authentic personality traits. Personality assessment plays a pivotal role in various fields, including psychology, education, social media, etc. However, traditional self-report questionnaires can only provide data based on what individuals are willing and able to disclose, thereby lacking objective. Moreover, automated measurements and peer assessments demand significant human effort and resources. In this paper, given the advantages of the Virtual Reality (VR) technique, we develop a VR simulator --- PersonalityScanner, to stimulate cognitive processes and simulate daily behaviors based on an immersive and interactive simulation environment, in which participants carry out a battery of engaging tasks that formulate a natural story of first-day at work. Through this simulator, we collect a synchronous multi-modal dataset with ten modalities, including first/third-person video, audio, text, eye tracking, facial microexpression, pose, depth data, log, and inertial measurement unit. By systematically examining the contributions of different modalities on revealing personality, we demonstrate the superior performance and effectiveness of PersonalityScanner.