The increasing concern on intelligent lighting designs for better life quality calls for the studies on thermal lighting environments. Given this background, this study investigated the effects of various ambient environmental settings on the physiological responses, psychological responses and work performance of subjects. A total of eight male university students performed a non-work task (30 min) and a work task (60 min) in various thermal lighting environments. The experimental conditions included a combination of five correlated colour temperatures (CCT) and two indoor temperatures (Temp). The galvanic skin response, heart rate, skin temperature, subjective evaluations and work performance were measured. The results showed that the ambient environments of CCT5000 and CCT6500 °K at 30 °C and CCT4000 °K at 28 °C significantly affected subjects’ physiology and psychology in both work and non-work tasks. The future lighting environment designs may refer these findings of the present study.