We report a detailed structural study of a series of five new quaternary Eu(II)-containing mixed chalcogenide phases, Eu2SiSe0.85S3.15, Eu2SiSe2.4S1.6, Eu2SiSe2.6S1.4, Eu2SiSe3.1S0.9, and Eu2SiSe4, synthesized using the flux-assisted boron chalcogen mixture (BCM) method. High-quality crystals were grown, and their crystal structures were determined by single-crystal X-ray diffraction. All members of the Eu2SiSexS4-x series crystallize in the monoclinic crystal system with space group P21/m, except Eu2SiSe4, which crystallizes in the P21 space group. The crystal structure of Eu2SiSexS4-x exhibits a complex three-dimensional network and is primarily composed of distorted trigonal prismatic EuQ6 polyhedra that are interconnected by SiQ4 tetrahedra. Polycrystalline powders were used for physical property measurements, including the magnetic susceptibility and UV-vis diffuse reflectance. Magnetic measurements indicated paramagnetic behavior with a slightly negative Weiss constant (θ = -13.54). The band gaps of the materials were determined from diffuse reflectance data, with optical band gaps estimated to be 2.04(2) eV, 1.98(2) eV, and 1.90(2) eV for Eu2SiSe0.85S3.15, Eu2SiSe2.6S1.4, and Eu2SiSe4, respectively. Band gap tuning was achieved by partially or fully replacing the S sites with Se.