Indoor daylighting quality has impacts on occupants’ physical and psychological aspects. Although daylighting design metrics have strictly restricted the amount of sunlight penetration, studies have shown occupants’ preference towards an appropriate amount of sunlight and distributions. Currently, insufficient studies have focused on the composition of interior daylighting distributions. Therefore, this paper presents a laboratory experiment exploring the psychological influences of sunlight patterns under immersive virtual reality scenes. The sunlight patterns are created by a combination of nine aperture designs, two window sizes and two sky types. The experiment collects 41 valid architecture students’ assessments and their physiological responses. Degrees of eight adjectives, including pleasantness, calmness, interest, excitement, complexity, spaciousness, satisfaction with exterior view amount and brightness, are rated by the participants. Physiological data of heart rates and electroencephalogram are collected. According to the analysis, both the aperture designs and sky types have influences upon subjective responses. The large window enhances beta oscillations and beta power on the right prefrontal lobe area, and the clear sky attenuates the theta rhythm on the pre frontal lobe areas. These findings indicate the important influence of natural lightscape compositions created by aperture designs and sky types upon occupants’ psychological processes.