Human outdoor thermal comfort is a complex perceptual process influenced by various factors, among which much attention has been given to physiological response, underscoring the need to equally focus on psychological perception. This study examines the psychological effects of Sky View Factor (SVF) and Green View Index (GVI) on pedestrian thermal comfort across spaces with similar microclimate, by conducting field surveys, climatic measurements, and a questionnaire survey involving 87 participants on October 22, 2022 in Shanghai. The results indicate that differences in SVF of about 8.6% and GVI of about 23.0% among independent points, as well as over 7.9% changes in GVI during a journey, significantly affect thermal sensation (p < 0.05, providing statistically significant evidence that these results are unlikely due to chance). Furthermore, the study suggests that under the influence of SVF and GVI, the general thermal sensation is influenced by the thermal sensation of the last point, as well as the averages and extremes (p < 0.001, p < 0.05, p < 0.001, respectively), while general thermal satisfaction correlates with average satisfaction levels (p < 0.05). These insights highlight the necessity of strategically designing SVF and GVI in urban outdoor spaces and offer valuable guidelines for urban planning to optimize pedestrian thermal comfort.