This work provides an investigation of the high pressure CO hydrogenation to higher alcohols on K2CO3 promoted active carbon supported molybdenum carbide. Both activity and selectivity to alcohols over supported molybdenum carbides increased significantly compared to bulk carbides in literatures. The optimal loadings of both molybdenum carbide and the K2CO3 promoter on active carbon have been investigated. The catalysts were characterized using BET surface area measurements, transmission electron microscopy and X-ray diffraction. Additionally, in-situ X-ray diffraction and in-situ X-ray absorption spectroscopy were applied for determining the carburization temperature and evaluating the composition of the carbide clusters of different samples through determinations of the Mo-C and Mo-Mo coordination numbers.