In this work, a chelating agent, ethylenediaminetetraacetic acid (EDTA) was used for the controllable synthesis of gold nanostructures in aqueous solution. Coral-shaped Au nanostructures were synthesized by reducing HAuCl4 with EDTA. EDTA serves not only as a reducing agent but also as a particle capping agent in the formation of coral-shaped Au nanostructures. It is found that the molar ratio of HAuCl4:EDTA and reacted temperature play significant effects on the formation and growth of these novel nanostructures. These Au nanostructures could serve as highly sensitive and reproductive surface-enhanced Raman scattering (SERS) substrates for chemical and biological detection.