Highly active and stable electrocatalysts for hydrogen evolution have been developed on the basis of molybdenum compounds (Mo2C, Mo2N, and MoS2) on carbon nanotube (CNT)–graphene hybrid support via a modified urea-glass route. By a simple modification of synthetic variables, the final phases are easily controlled from carbide, nitride to sulfide with homogeneous dispersion of nanocrystals on the CNT–graphene support. Among the prepared catalysts, Mo2C/CNT–graphene shows the highest activity for hydrogen evolution reaction with a small onset overpotential of 62 mV and Tafel slope of 58 mV/dec as well as an excellent stability in acid media. Such enhanced catalytic activity may originate from its low hydrogen binding energy and high conductivity. Moreover, the CNT–graphene hybrid support plays crucial roles to enhance the activity of molybdenum compounds by alleviating aggregation of the nanocrystals, providing a large area to contact with electrolyte, and facilitating the electron transfer.