The crude glycerol from biodiesel production possesses low economic values and alternative ways of converting it to valuable chemicals are needed to sustain the biodiesel industry. This study aimed to investigate the production of primary alcohols and propylene glycol from glycerol through a catalytic thermochemical process without an external supply of hydrogen. The effects of reaction time, water to glycerol ratio, and doses of catalyst on glycerol conversion and alcohol yields were investigated using a batch pressure reactor and Raney nickel catalyst. The presence of alcohols and gases in the products confirmed that hydrogen was produced and was utilized in the formation of propylene glycol through hydrogenolysis. Ethanol and propylene glycol yields of up to 10.4 +/- 0.2 and 33.2 +/- 1.4 mol %, respectively, were observed. It was also concluded that ethanol is formed through hydrogenolysis of propylene glycol and its yield improves at extended reaction time and increased initial water content of the feed.