The effect of sodium doping on alumina and zirconia activity in methanethiol formation from hydrosulphurisation of methanol by H2S was studied. It provoked an activity decrease and a selectivity increase in agreement with the catalysts basicity increase. By contrast, molybdenum doped zirconia samples presented a higher activity but a lower selectivity than pure zirconia, as expected from their higher acidity. Increase of the CH3OH/H2S ratio in the reaction mixture improved both activity and CH3SH selectivity. It was found that zirconia loaded with small amounts of molybdenum working under H2S excess shows good performances towards CH3SH production.