Gelcasting has been extensively studied and applied as a near-net-shaping technique for preparing complex ceramic parts. However, the use of acrylamide as a main component is an important drawback of this method as it is a hazardous, neurotoxic compound. In this context, a new low-toxicity monomer, glycerol monoacrylate, has been synthesized and successfully used for the gelcasting of ceramic suspensions. The presence of two hydroxyl groups in a monomer molecule allows the formation of a polymer network by the monomer polymerization and cooperative hydrogen bonding without any external crosslinking agent. The stability and rheological behavior of alumina gelcasting suspensions containing the new monomer has been studied by oscillatory measurements under the controlled deformation mode. The results were compared with those obtained for commercially available monomers, 2-hydroxyethyl acrylate and diethylene glycol diacrylate used as a crosslinking agent, in which case the effect of an initiator and activator was studied. The gelcasting performance for both the commercial and the newly synthesized monomers was studied and compared, showing that the former allows a faster gelation, whereas the latter leads to more uniform microstructures and higher sintered densities of up to 99% of TD.