Black peppercorn is a common ingredient imported and used in uncooked or ready-to-eat foods in the United States. They might be exposed to fecal coliforms and other microbial contamination due to a lack of good agricultural and manufacturing practices in some developing countries under which they were grown and harvested, thus causing economic losses to the peppercorn industry in the United States. We investigated the effect of gaseous chlorine dioxide (ClO2) on reducing the microbial population levels of coliforms, aerobic bacteria, yeasts, and molds on unprocessed black peppercorns. Treatments on peppercorns were conducted in a 30-L airtight chamber, and equal amounts of dry media precursors were used to generate gaseous ClO2. Whole peppercorns (200 g) were exposed to 20, 30, and 40 g of precursor dose for up to 60 min at 21 ± 0.4°C and in combination with mild heat at 40 ± 2°C. Aerobic bacteria, coliforms, yeasts, and molds on peppercorns were enumerated before (7.4, 7.2, and 7.1 log CFU/g, respectively) and after treatments. Results after treatment demonstrated 0.8–1 log10 (90%) reduction for all the microbes post-treatment at 21 ± 0.4°C. The treatments conducted with a 30 g precursor dose for 60 min at 21 ± 0.4°C reduced statistically higher (p < .05) microorganisms than those at 40 ± 2°C. Our work demonstrated that gaseous ClO2 could be used as a part of an overall hurdle technology to reduce the coliforms, aerobes, yeasts, and molds on black peppercorns without affecting the visual quality.