Wearing a silicone wristband exposes the internal surface of the wristband to glucose, lipids, and metabolites (metabolome) found in sweat and the external surface to occupational and environmental factors that could impact health found in the air (exposome). We use silicone wristband electrospray ionization mass spectrometry (SWESI‐MS) to monitor these species. A 20‐μL drop of a (1 : 1, v/v) water:methanol solution is sufficient to extract abundant metabolites and contacting chemicals derived from ingestion of drink, smoke, diet, drug, and air pollution exposure. A wide coverage of species is successfully detected and identified from a worn wristband including caffeine, glucose, nicotine, reserpine, lactate, phosphocreatinine, oleic acid, and urea. The signal from a triangular wristband surface triggered by applying a voltage of 5 kV to form a spray remains stable for at least 2 minutes. The response is linear from 10 pM to 100 μM. The SWESI‐MS method offers the advantages of onsite sampling, no preprocessing, simple testing, and automatic high‐dimensional data searching. It can be used for simultaneously monitoring hazardous chemical contamination and abnormal expression of sweat‐secreted metabolites that are indicative of some physiological condition.