As most of the occupants spend approximately 90% of their time indoors (Klepeis et al., 2001), especially because of the COVID-19 pandemic (Lee et al., 2020), they expect more satisfaction in the indoor environment. Due to the limited daylight available in indoor spaces, however, their satisfaction is not high enough. Especially, students are dissatisfied when they study in a classroom without daylight, and many studies have examined that students have better learning skills in classrooms with daylight through windows (Hathaway, 1992; Heschong, 1999). Therefore, daylight and biomimicry are the most critical factors for occupants’ satisfaction in an indoor educational environment. According to a previous study (Son, 2020), a novel strategy has been proposed to bring daylight into non-window spaces using biomimetic solutions inspired by polar bears’ hair. The purpose of this study was to examine the enhancement of occupants’ satisfaction in virtual reality (VR) environment with the proposed novel biomimetic window system in a university library. Furthermore, since the proposed biomimetic window system is not an existing system, a VR experiment was conducted to see how the satisfaction of the students changed. This study created six different VR environments and used a VR headset for the participants to experience the built virtual environments. A 360-degree panoramic camera captured open space and enclosed space at the university library, and three conditions were given to each space: 1) Condition with no window, 2) Condition with biomimetic window and allowed daylight into the space, and 3) Condition with biomimetic window and allowed daylight and nature view. Before conducting the VR experiments, the study calculated RGB and Kelvin values of each condition to minimize bias by the color of light in each virtual space. The study also created a questionnaire using a five-point Likert scale. The 56 participants were asked about their impressions, daylighting impact, and seating preference in each environment. In addition, the survey asked about their feeling and the number of hours they could study in each space. At the end of the survey, students were asked about their age, gender, and average hours they usually spend for study. The results showed how students’ preferences changed when the biomimetic window system was installed. Students were more satisfied with the room where the daylight entered through the biomimetic window system than where the window did not exist. It also showed a slightly positive perception when the daylight and the view were seen together than when only the daylight entered the room. The study also found the students’ preferred space when the biomimetic window system was installed. When the biomimetic window system was installed, students preferred the enclosed space over the open space. However, the results indicated that the preference of each space according to students’ average study time was not correlated. The study adopted one of the biomimicry strategies and tested students’ satisfaction with daylight in an educational environment using a VR system. The results showed that the daylighting brought by the novel biomimetic window system helped students increase their satisfaction.