The influence of Mg doping on structural, magnetic and optical characteristics of Gd2FeCrO6, Gd2Fe0.75Mg0.25CrO6 and Gd2FeCr0.75Mg0.25O6 double perovskites has been systematically investigated. The monoclinic crystal structure with the P21/n space group is confirmed by powder X-ray diffraction data. From the scanning electron microscopy graphs, we noticed few nearly spherical and dumbbell-shaped grains for all compounds with an average grain size of about 76 - 85 nm. The magnetic studies demonstrated the presence of a weak ferromagnetic transition with antiferromagnetic background at low temperatures for all the samples. A decrement in the transition temperature of Gd2FeCrO6 (TC = 8.14 K) is observed on Mg doping, which is due to the smaller ionic radii of Mg at the Fe/Cr site in Gd2Fe0.75Mg0.25CrO6 and Gd2FeCr0.75Mg0.25O6 double perovskites. By analyzing the UV–visible spectroscopic absorption data, direct band gaps around 3 eV are concluded for pure and Mg doped Gd2FeCrO6 double perovskites, validating their application in wastewater photocatalysis.