ABSTRACT Silver nanoparticles have been synthesized in a new hierarchical shape using simple electrospinning technique and novel hydrothermal treatment process. A sol-gel consisting of poly(vinyl alcohol) and silver nitrate has been electrospun to produce nanofiber mats which were dried under vacuum at room temperature for 24 h. The dried nanofiber mats have been hydrothermally treated by novel strategy. The treatment process was based on producing of water gas (CO and H2) to eliminate the polymer and to reduce the silver nitrate into silver metal. The process was carried out by heating the dried nanofiber mats at 300 oC for 30 min in an especially designed reactor in which a stream of water vapor was passing through an activated carbon bed. X-Ray diffraction pattern (XRD) and thermal gravimetric analysis (TGA) have affirmed that the proposed treatment methodology has been completely eliminated the utilized polymer and decomposed silver nitrate into pure silver. Moreover, scanning electron microscope images revealed that the obtained product have novel nanostructure; leaves of date tree shapes. According to the wide application of silver nanostructures, the newly obtained shape may have especial interest to be invoked in several applications.