The catalytic hydroalkoxylation of butadiene with glycerol has been performed for the first time thanks to the use of nickel catalysts and an appropriate solvent. Optimization of the reaction conditions allowed obtaining 100% glycerol conversion into a mixture of glyceryl mono- and dibutenyl ethers. The experimental protocols used involved batch experiments or continuous feeding of butadiene at atmospheric pressure. The reaction has then been scaled up to produce multigrams of each pure monoethers and diethers according to simple decantation/distillation procedures. The ethers were further hydrogenated to their corresponding alkyl glyceryl ethers.