The rapid speed of urbanization in modern cities has led to various environmental challenges impacting human activities, livelihoods, and comfort. One of these effects is the urban heat island, which describes the increase in temperature in an urban area resulting from the replacement of natural surfaces with concrete, buildings, and other structures that absorb and retain heat. Variations in individual perception and adaptative ability present additional challenges when trying to ensure outdoor comfort and require advanced measuring instruments and simulation tools to accurately predict a broad range of related variables. In this study, we investigated three different types of blue–green spaces (six in total) on the campus of Guangzhou University, focusing on their distinct layouts. The aim was to evaluate these spaces’ microclimate and sunlight intensity conditions by quantifying several environmental factors. Subjective comfort assessments and objective physiological parameter measurements were conducted using questionnaires and biosensors, respectively. The results revealed the following: (1) Different types of blue–green spaces exhibit distinct microclimate and visual environment characteristics, and while similar patterns emerged, certain environmental parameters revealed important differences. (2) There is a significant association between individuals’ thermal and visual comfort in blue–green spaces and multiple environmental factors. (3) Linear regression analysis demonstrated the strong predictive capabilities of skin conductance indicators (Rsc, SCR, and nSCR) in assessing individuals’ outdoor visual–thermal comfort levels, with R2 exceeding 0.5, indicating high accuracy. These findings provide valuable insights and references for urban planners and designers seeking to enhance the visual and thermal aspects of sustainable landscapes on campuses as well as in other outdoor environments.