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An effective control of the properties in polycrystalline materials continues to be the one of the most difficult challenges for the modern materials science. It is well known that the properties of polycrystalline materials are mostly defined by their structure and the interfaces that they contain, particularly by the grain boundaries (GB). The goal of this work is to investigate the relationship between geometrical characteristics (misorientation, inclination) of GBs and their energy using the model binary metal Zn–Sn system. Zn–2 wt. % Sn alloy samples have been prepared by melting in argon, air quenching, and cold-rolling. Then samples were annealed above eutectic temperature at 210°C and water quenched to retain the structure which formed during the annealing. The microstructure of the polycrystalline specimens was studied by scanning electron microscopy and electron back-scattering diffraction. Crystal orientations of more than 1000 individual zinc grains were determined in the form of Euler angles. The grain boundary misorientations between the neighboring grains were calculated using the quaternions based algorithm. Experimentally obtained values of the Sn(Zn) melt–Zn solid dihedral angles were used to estimate the energy of corresponding Zn grain boundaries neglecting the anisotropy of solid-liquid interfacial energy. Correlation between geometrical characteristics and energy of Zn GBs was observed and discussed. The financial support of Russian Foundation for Basic Research (contracts 11-08-01244-а and 11-08-90439) is acknowledged.