Although post-processing is relative complex, which may affect the purity of products, these unconventional methods are surely efficient and powerful. Therefore, in the review we will introduce some other unconventional multistep methods which can synthesize shape-controlled and novel silver nanostructures including the double reductants method, etching technique and construction of core-shell nanostructures. Jones et al.  covered a number of templates for the preparation of plasmonic nanostructures including solution-phase templates, porous templates and surface mask templates. They have mentioned part of the etching technique and core-shell nanostructures in their review. However, we reviewed these unconventional methods from three perspectives following different rules. The double reductant method is based on different favorable facets of silver nanocrystals produced in different reductants. The etching technique involves the use of an etchant to selectively remove nanoparticles so that nanostructures can be obtained with shape control. The mechanism of construction of core-shell nanostructures is epitaxial selleck chemical growth from core seeds. The optical properties of these nanostructures can be finely tuned corresponding to the shape and size control leading to wide range of potential applications.2.?Double Reductant MethodIt is known that different reductants can offer different reducibility, which plays an important role in shape control of nanostructures. Moreover, favorable facets of nanocrystals are determined by the reductants used. Some reductants prefer to promote growth of (100) facets, while others prefer to (111) or (110) facets. Therefore, complex nanostructures or nanostructures which are not easy to be prepared using one-step methods can be obtained by choosing different reductants in each step leading to desired nanostructures.2.1. N,N-dimethylformamide (DMF) and EGDMF is a well-known organic solvent as well as an active reductant under suitable condition which has been demonstrated . Liz-Marz��n’s group first employed DMF to reduce AgNO3 for the preparation of silver nanostructures which paved a new way for shape control . In their later works, they successfully synthesized nanospheres , nanoprisms [34,35] and nanowires  via reduction of AgNO3 by DMF in the presence of PVP. In addition, Gao et al.  prepared silver decahedrons in high yield with PVP as stabilizer in DMF. Tsuji et al.  provided new information on the growth of decahedrons and icosahedrons in DMF through a stepwise route. Lu et al.  realized the finely tuned size of nanoplates from 20 to 50 nm by varying the molar ratio of PVP/DMF.