In frames of this work a series of ZnWO4 single crystals, pure and doped with either Ca (5 at%) or Ca (4 at%) and Eu (1 at%), has been grown by the Czochralski method. Phase analysis and structural refinement was performed X-ray powder diffraction and the powder diffraction and the patterns were analyzed by the Rietveld refinement method to analyze the lattice parameters of the crystal structure. Additionally, the absorbance, photoluminescence emission (PL) and photoluminescence excitation (PLE) and EPR spectra were measured and compared to investigate influence of Ca and Eu co-doping on optical properties of the obtained crystals. Furthermore the optical band-gap of the crystals has been calculated. The crystal structure of all mentioned ZnWO4 samples has also discussed in the scope of environment symmetry and possible sites of dopant ions. (C) 2016 Elsevier B.V. All rights reserved.