A novel vapor phase production process for CF3I was successfully developed for the reaction between CHF3 with I-2 in the presence of a unique catalyst. The most effective catalyst system for this reaction was found to be alkali metal salts which were supported on an activated carbon carrier. A consideration of the reaction mechanism suggests that the reaction proceeds via CF2 carbenes formed on the catalyst surface as intermediates, followed by carbene disproportionation to CF3 radicals, followed by reaction with I-2 to give CF3I. (C) 2003 Elsevier B.V. All rights reserved.