Excess crude glycerol derived as a by-product from biodiesel industry prompts the need to valorise glycerol to value-added chemicals. In this context, catalytic steam reforming of glycerol (SRG) was proposed as a promising and sustainable alternative for producing renewable hydrogen (H-2). Herein, the development of nickel (Ni) supported on ceria-modified mesoporous gamma-alumina (gamma-Al2O3) catalysts and their applications in catalytic SRG (at 550-750 degrees C, atmospheric pressure and weight hourly space velocity, WHSV, of 44,122 ml.g(-1).h(-1) (STP)) is presented. Properties of the developed catalysts were characterised using many techniques. The findings show that ceria modification improved Ni dispersion on gamma-Al2O3 catalyst support with highly active small Ni particles, which led to a remarkable catalytic performance with the total glycerol conversion (ca. 99%), glycerol conversion into gaseous products (ca. 77%) and H-2 yield (ca. 62%). The formation rate for H-2 production (14.4 x 10(-5) mol.s(-1).g(-1), TOF (H-2) = 3412 s(-1)) was significantly improved with the Ni@12Ce-Al2O3 catalyst, representing nearly a 2-fold increase compared with that of the conventional Ni@Al2O3 catalyst. In addition, the developed catalyst also exhibited comparatively high stability (for 12 h) and coke resistance ability. (C) 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.