Students often experience high levels of daily academic pressure, spending extended periods within indoor classroom environments. Windows, as a medium of proximity to nature, play an important role in relieving stress. However, the broader implications of the Window Green View Index (WGVI) on individual well-being remain underexplored. This study aims to assess the effects of WGVI on stress recovery in college students by utilizing virtual reality technology to create five classroom environments with varying WGVI levels: 0%, 25%, 50%, 75%, and 100%. Twenty-four participants were subjected to the Trier Social Stress Test before engaging with the different WGVI scenarios for stress recovery. Both subjective assessments and objective physiological indicators were evaluated. Results indicated that participants exhibited the lowest Profile of Mood States (POMS) score (−4.50) and significantly improved systolic blood pressure recovery at a 25% WGVI level. The examination of EEG data revealed that the O2 channel in the occipital region exhibited the highest level of activity in the alpha frequency range during the experiment. Additionally, a significant association was observed between the EEG measurements and the subjective rating of stress. This study underscores the significance of incorporating WGVI into the design and planning of college buildings to promote mental health and well-being among students.