Catalytic chlorination of methane was studied over SO42-/ZrO2, Pt/SO42-/ZrO2, and Fe/Mn/SO42-/ZrO2 solid superacid catalysts. The reactions were carried out in a continuous flow reactor under atmospheric pressure, at temperatures below 240-degrees-C, with a gaseous hourly space velocity of 1000 ml/g h and a methane to chlorine ratio of 4 to 1. At 200-degrees-C with 30% chlorine converted the selectivity in methyl chloride exceeds 90%. At more elevated temperatures, the selectivity decreases but stays above 80% in methyl chloride at 225-degrees-C using the sulfated zirconia catalysts. The selectivity can be enhanced by adding platinum to sulfated zirconia catalysts. An iron and manganese-doped catalyst exhibited excellent selectivities at somewhat lower conversions. Methyl chloride is obtained at 235-degrees-C in selectivities greater than 85%. No chloroform or carbon tetrachloridc is formed. The electrophilic insertion involves electron-deficient metal-coordinated chlorine into the methane C-H bond.