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Study of hydrogen production from aqueous glycerol solution using RuO2-loaded LaNaTaO3 photocatalyst is reported in this paper. This research aims to investigate the influence of RuO2 co-catalyst and glycerol as a sacrificial reagent on photocatalytic process of hydrogen production. La-doped NaTaO3 was prepared via sol-gel route. The RuO2 was loaded onto the LaNaTaO3 surface by impregnation method. The sample were characterized by Scanning Electron microscopy (SEM) and X-ray diffractometer (XRD). The XRD spectrum shows that the La-NaTaO3 photocatalyst has high crystallinity. The SEM analysis indicates that the size of La-NaTaO3 photocatalyst is ranging from 100 to 250 nm without agglomeration and RuO2 as a co-catalyst is well loaded into the La-NaTaO3 surface. Loading RuO2 on La-NaTaO3 photocatalyst is proven to increase the rate of hydrogen production by 9.8 times with addition of glycerol as a sacrificial reagent. The highest hydrogen production activity was obtained at 0.3 wt.% ruthenium loading and increase significantly with increasing glycerol concentration. The role of co-catalyst RuO2 and glycerol as sacrificial reagent enhanced the performance of La-NaTaO3 photocatalyst by playing an active role in the separation efficiency of electrons and holes and the reaction of hydrogen formation.