Introduction: Air pollution has numerous impacts on human health on a variety of time scales. Pollutants such as particulate matter—PM1 and PM2.5, carbon dioxide (CO2), nitrogen dioxide (NO2), and nitric oxide (NO) are exemplars of the wider human exposome. In this study, we adopted a unique approach by utilizing the responses of human autonomic systems to gauge the abundance of pollutants in inhaled air. Objective: To investigate how the human body autonomically responds to inhaled pollutants in microenvironments, including PM1, PM2.5, CO2, NO2, and NO, on small temporal and spatial scales by making use of biometric observations of the human autonomic response. To test the accuracy in predicting the concentrations of these pollutants using biological measurements of the participants. Methodology: Two experimental approaches having a similar methodology that employs a biometric suite to capture the physiological responses of cyclists were compared, and multiple sensors were used to measure the pollutants in the air surrounding them. Machine learning algorithms were used to estimate the levels of these pollutants and decipher the body’s automatic reactions to them. Results: We observed high precision in predicting PM1, PM2.5, and CO2 using a limited set of biometrics measured from the participants, as indicated with the coefficient of determination (R2) between the estimated and true values of these pollutants of 0.99, 0.96, and 0.98, respectively. Although the predictions for NO2 and NO were reliable at lower concentrations, which was observed qualitatively, the precision varied throughout the data range. Skin temperature, heart rate, and respiration rate were the common physiological responses that were the most influential in predicting the concentration of these pollutants. Conclusion: Biometric measurements can be used to estimate air quality components such as PM1, PM2.5, and CO2 with high degrees of accuracy and can also be used to decipher the effect of these pollutants on the human body using machine learning techniques. The results for NO2 and NO suggest a requirement to improve our models with more comprehensive data collection or advanced machine learning techniques to improve the results for these two pollutants.