A set of novel bio-based star-shaped thermoset resins was synthesized via ring-opening polymerization of lactide and employing different multi-hydroxyl core molecules, including ethylene glycol, glycerol, and erythritol. The branches were end-functionalized with methacrylic anhydride. The effect of the core molecule on the melt viscosity, the curing behavior of the thermosets and also, the thermomechanical properties of the cured resins were investigated. Resins were characterized by Fourier-transform infrared spectroscopy, 13C-NMR, and 1H-NMR to confirm the chemical structure. Rheological analysis and differential scanning calorimetry analysis were performed to obtain the melt viscosity and the curing behavior of the studied star-shaped resins. Thermomechanical properties of the cured resins were also measured by dynamic mechanical analysis. The erythritol-based resin had superior thermomechanical properties compared to the other resins and also, lower melt viscosity compared to the glycerol-based resin. These are of desired characteristics for a resin, intended to be used as a matrix for the structural composites. Thermomechanical properties of the cured resins were also compared to a commercial unsaturated polyester resin and the experimental results indicated that erythritol-based resin with 82% bio-based content has superior thermomechanical properties, compared to the commercial polyester resin. Results of this study indicated that although core molecule with higher number of hydroxyl groups results in resins with better thermomechanical properties, number of hydroxyl groups is not the only governing factor for average molecular weight and melt viscosity of the uncured S-LA resins.