We describe a facile growth of chain-like Au nanostructures and their spontaneous transformation to multi-twined nanostructure using a mild reducing agent bisphenol A (BPA). The growth Au nanostructures involves the chemical reduction of HAuCl₄ by BPA in the presence of cetyltrimethylammonium bromide (CTAB) as capping agent in alkaline condition without any seeds. Wire and chain-like Au nano-network structures with diameter in the range of 4 to 9 nm are obtained in the initial stage of the reaction. These chainlike nanostructures undergo spontaneous transformation into multi-twined nanostructures within 24 h. These nanocrystalline multi-twined structures have an average size of 80-90 nm. X-ray and selected area electron diffraction measurements reveal that the Au nanoparticles have (111), (200), (220) and (311) planes of a face centered cubic structure. High resolution transmission electron microscopic measurement shows that the nanostructures are mainly composed of (111) lattice plane with twin boundaries. The concentration of HAuCl₄, BPA and CTAB has pronounced effect in the growth of nanostructures. The multi-twined nanostructures are highly stable at room temperature over a period of one month and can be used for catalytic applications.