Abstract: Single crystals of Cu2ZnSn(SxSe1-x)4 (CZTSSe) solid solutions have deen grown by chemical vapor transport technique using ICl3 as a transport agent. Analyzing the X-ray diffraction patterns reveal that the as-grown CZTSSe solid solutions are crystallized in kesterite structure and the lattice parameters are determined. The S contents of the obtained crystals are estimated by Vegard’s law. The composition dependent band gaps of CZTSSe solid solutions are studied by electrolyte electroreflectance (EER) techniques. The band gaps of CZTSSe are evaluated by a lineshape fit of the EER spectra and are found to increase almost linearly with the increase of S content.