Accumulated evidence claims that urban green spaces (UGS) have a positive impact on the physical and mental health of humans. However, little information is available to clearly reveal what the most important driving factors are for human psychophysiological restoration. In order to unveil this uncertainty, this study employed virtual reality (VR) technology to investigate the physiological (electroencephalogram, EEG), and psychological (attention, positive mood, negative mood) responses and individual preferences for different urban environments. Participants (120) were recruited and randomly assigned to experience six different types of environments varying in land use and vegetation structures, which were: Grey space, blue space, open green space, partly open green space, partly closed green space, and closed green space. The results showed that the experience of the six environmental types through VR devices had positive restorative effects on the individuals’ attentional fatigue and negative mood; however, all the participants obtained the highest levels of physiological stress restoration when asked to close their eyes for relaxation. The physiological measurements of the EEG showed no significant differences among the selected types of environments. Meanwhile, the results of the psychological measures suggested that only negative mood showed significant differences of change among the six types of environments, and while the partly open green space had the most positive effect on negative mood, the closed green space had the worst. The blue space and partly closed green space received higher recreational preference ratings than the other four environments, while the closed green space received the lowest recreational preference rating. Moreover, the findings showed that there was a strong positive correlation between people’s preferences and the improvement of their positive mood. This indicated that as the popularity of a natural environment increased, so did the benefits of human health and well-being. In addition, this study shows that VR technology may be utilized as a possible surrogate measure to real scenes in evaluating human physiological and psychological restoration in the future. The present findings can provide the theoretical basis and practical guidance for future optimal planning of urban restorative environments.