Silver nano-hexagons (AgNHs) have been prepared by a chemical reduction method using poly-vinyl pyrrolidone (PVP) as a stabilizing agent. The XRD results exhibit the crystalline nature of the prepared sample, with a face centred cubic (fcc) phase. Transmission electron microscopic (TEM) results reveal that the silver nanoparticles are nearly hexagon in shape with an average size of 50 nm. Here, crystallite size has been calculated using Williamson-Hall (W-H) method, which is nearly matching with average size obtained from TEM analysis. Again, using W-H method, micro strain has been calculated, which is produced in the nano-hexagon due to dislocation of silver atoms. Further, the lattice constant of the nano-hexagons has also been estimated from the Nelson–Riley plot. Moreover, the appropriate structural parameters such as Lorentz factor, Lorentz polarization factor, dislocation density, number of atoms in a unit cell and morphological index have also been studied from the X-ray diffraction profile.