A comparative analysis of the structure of silver nanoparticles obtained by chemical synthesis (citrate method) and electrical explosion of wires is carried out. The structure, phase composition, lattice parameters of silver nanoparticles with sizes from 2 to 50 nm were studied by electron diffraction and high-resolution transmission electron microscopy. All silver nanoparticles obtained by the chemical method have only a cubic structure. Silver nanoparticles obtained by the physical method have cubic and hexagonal structures. The existence of the hexagonal phase under normal conditions is explained by the quenching effect. The lattice parameters of the cubic phase of Ag NPs within the experimental determination error (± 0.01 nm), synthesized by the chemical method and by the method electrical explosion of wires do not differ from each other.