A study of catalyst pre-sulfiding for the synthesis of 3-methylthiophene from 2-methylbutanol and carbon disulfide over potassium-promoted chromia-alumina has been performed. Pretreatment with CS2 results in enhancements in 3MT yield and catalyst lifetime. The benefits observed are ascribed to a combination of enhanced Cr2S3 formation and poisoning of sites responsible for side reactions which limit selectivity and result in the formation of deactivating by-products.