The Tiptop underground coal-mine fire in the Skyline coalbed of the Middle Pennsylvanian Breathitt Formation was investigated in rural northern Breathitt County, Kentucky, in May 2008 and January 2009, for the purpose of determining the concentrations of carbon dioxide (CO2), carbon monoxide (CO), and mercury (Hg) in the vent and for measuring gas-vent temperatures. At the time of our visits, concentrations of CO2 peaked at 2.0% and > 6.0% (v/v) and CO at 600 ppm and > 700 ppm during field analysis in May 2008 and January 2009, respectively. For comparison, these concentrations exceed the U.S. Occupational Safety & Health Administration (OSHA) eight-hour safe exposure limits (0.5% CO2 and 50 ppm CO), although the site is not currently mined. Mercury, as Hg0, in excess of 500 and 2100 μg/m3, in May and January, respectively, in the field, also exceeded the OSHA eight-hour exposure limit (50 μg/m3). Carbonyl sulfide, dimethyl sulfide, carbon disulfide, and a suite of organic compounds were determined at two vents for the first sampling event. All gases are diluted by air as they exit and migrate away from a gas vent, but temperature inversions and other meteorological conditions could lead to unhealthy concentrations in the nearby towns. Variation in gas temperatures, nearly 300 °C during the January visit to the fire versus < 50 °C in May, demonstrates the large temporal variability in fire intensity at the Tiptop mine. These preliminary results suggest that emissions from coal fires may be important, but additional data are required that address the reasons for significant variations in the composition, flow, and temperature of vent gases.