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.