A fast microwave-assisted method is reported for the synthesis of CaCO3 (vaterite) with various morphologies in the water/ethylene glycol (EG) system with surfactants. Our experiments show that microwave heating, reaction time, surfactant, and the water-EG mixed solvents play important roles in the morphology of vaterite. Vaterite with dagger-like, bicone-like, shuttle-like morphology and microspheres self-assembled from nanoparticles have been obtained by adjusting the experimental parameters. The products were characterized by X-ray powder diffraction, transmission electron microscopy, and scanning electron microscopy.