Diesel fuel is commonly used for underground mining equipment, yet diesel engine exhaust is a known human carcinogen. Alternative fuels, including biodiesel, and a natural gas/diesel blend, offer the potential to reduce engine emissions and associated health effects. For this pilot study, exposure monitoring was performed in an underground mine during operation of a load-haul-dump vehicle. Use of low-sulfur diesel, 75% biodiesel/25% diesel blend (B75), and natural gas/diesel blend (GD) fuels were compared. Personal samples were collected for total and respirable diesel particulate matter (tDPM and rDPM, respectively) and total and respirable elemental and organic carbon (tEC, rEC, tOC, rOC, respectively), as well as carbon monoxide (CO), formaldehyde, acetaldehyde, naphthalene, nitric oxide (NO), and nitrogen dioxide (NO2). Compared to diesel, B75 use was associated with a 33% reduction in rDPM, reductions in rEC, tEC, and naphthalene, increased tDPM, tOC, and NO, and no change in rOC, CO, and NO2. Compared to diesel, GD was associated with a 66% reduction in rDPM and a reduction in all other exposures except CO. The alternative fuels tested both resulted in reduced rDPM, which is the basis for the current Mine Safety and Health Administration (MSHA) occupational exposure standard. Although additional study is needed with a wider variety of equipment, use of alternative fuels have the promise of reducing exposures from vehicular exhaust in underground mining settings.