Montmorillonite (MMT) dispersed g-C3N4/TiO2 hybrid nanocomposite for enhanced photo-catalytic hydrogen production from glycerol-water mixture has been investigated. The newly designed composite photo-catalysts were fabricated through a sol-gel assisted hydrothermal method and were characterized by XRD, XPS, SEM, EDX, TEM, FTIR, UV-Vis, Raman and PL spectroscopy. Well-designed g-C3N4/MMT/TiO2 heterojunction composite was obtained with 2D MMT structure, which promoted both visible light absorption and hindered charges recombination rate. The modification of 2D/0D g-C3N4/TiO2 heterojunction with 2D MMT sheets enhances H-2 production due to MMT works as a mediator for effective charges trapping and transportation within the composite structure. The g-C3N4/MMT/TiO2 photo-catalyst exhibits highest H-2 production of 4425 ppm h(-1) g(-1) at pH 7.0, which was 2.12 times higher than the pure TiO2 (2085 ppm h(-1) g(-1)). In addition, increasing catalyst loading promotes more H-2 evolution and among the different sacrificial reagents, glycerol-water mixture gave highest H-2 production due to the presence of alpha-hydrogen atoms attached to carbon atoms. The enhanced photocatalytic efficiency can be attributed to synergistic effect of MMT with g-C3N4/TiO2 heterojunction composite, appropriate band structure and transportation of electrons-holes with their hindered recombination rate. These composite catalysts exhibited excellent photo-catalytic stability for H-2 production in cyclic runs. Possible reaction mechanism for hydrogen production over g-C3N4/MMT/TiO2 composite has been explained based on the experimental results. The finding of this work would be fruitful for hydrogen production applications with all sustainable systems.