Humans are the primary sources of CO2 and NH3 indoors. Their emission rates may be influenced by human physiological and psychological status. This study investigated the impact of physiological and psychological engagements on the human emissions of CO2 and NH3. In a climate chamber, we measured CO2 and NH3 emissions from participants performing physical activities (walking and running at metabolic rates of 2.5 and 5 met, respectively) and psychological stimuli (meditation and cognitive tasks). Participants' physiological responses were recorded, including the skin temperature, electrodermal activity (EDA), and heart rate, and then analyzed for their relationship with CO2 and NH3 emissions. The results showed that physiological engagement considerably elevated per-person CO2 emission rates from 19.6 (seated) to 46.9 (2.5 met) and 115.4 L/h (5 met) and NH3 emission rates from 2.7 to 5.1 and 8.3 mg/h, respectively. CO2 emissions reduced when participants stopped running, whereas NH3 emissions continued to increase owing to their distinct emission mechanisms. Psychological engagement did not significantly alter participants' emissions of CO2 and NH3. Regression analysis revealed that CO2 emissions were predominantly correlated with heart rate, whereas NH3 emissions were mainly associated with skin temperature and EDA. These findings contribute to a deeper understanding of human metabolic emissions of CO2 and NH3.