To model individuals' experience of urban spaces, this study integrates knowledge from environmental psychology and artificial intelligence to propose a framework for individuals' perceptions and emotion by incorporating individual characteristics and cognitive appraisal together with environment attributes as determinants. A path model is employed to capture how the four perceptions of environmental qualities (safety, liveliness, comfort, and legibility) and three dimensions of emotion (pleasure, arousal, dominance) are influenced by individual characteristics and cognitive appraisal using data collected in an online virtual reality experiment with 237 participants. Results show that emotional pleasure is more directly influenced by environmental attributes while arousal and dominance are closely related to a person's current mood and personality. Perceptions of environmental qualities do have mediating effects in emotion generation, but contribute differently to the three dimensions of emotion. Cognitive appraisal variables directly influence emotion generation, with ideal values always having positive effects and expected values always negative effects. The findings can help capture the dynamic process of emotional experiences between diverse individuals and may support experience-centered simulation and prediction.