This work investigated low shrinkage curing techniques and characterization of unsaturated polyester (UPE-8340) and vinyl ester (VE-922) reinforced composite. The reinforced polymeric composite was composed using various amounts (0.1 vol.% to 0.5 vol.%) of methyl ethyl ketone peroxide (MEKP) and the proportion of UPE and VE (5 vol.%) was kept fixed throughout the study. The epoxy matrix was formed using a 3D printed acrylonitrile butadiene styrene (ABS) dumbbell shape mold and the specimen was cured in the presence of air and an inner gas (carbon dioxide) using a customized ambient closed chamber system. The influence of MEKP on UPE and VE reinforce composites was studied by investigating curing kinetics, shrinkage, tensile properties, contact angle, and thermal stability. The CO2-cured results show a significant lower shrinkage rate and higher tensile strength and flexural modulus of UPE and VE reinforced composite articles compared with air-cured reinforced composite. These macro-scale results correlate with the air-cured structure, an un-banded smooth surface was observed, and it was found that the lowest amount of MEKP revealed significant improvement in the contact angle of UPET and VE reinforced composites.