A double perovskites Ba0.5Rb0.5LaTeO6 and Ba0.5Rb0.5La0.9Sm0.1TeO6 were synthesized by a solid-state reaction method. The structural properties were studied by using the X-Ray powder diffraction (XRD) and fourier transform infrared spectroscopy (FTIR). Structural analysis of XRD based on Rietveld refinement indicates that the Ba0.5Rb0.5LaTeO6 and Ba0.5Rb0.5La0.9Sm0.1TeO6 have cubic symmetry with space group Fm m. The tolerance factor of the sample also decreases with Sm3+ substitution. The value obtained from tolerance factor for Ba0.5Rb0.5LaTeO6 and Ba0.5Rb0.5La0.9Sm0.1TeO6 was 0.994 and 0.982 respectively. The optical properties were studied using the UV visible absorption spectroscopy (UV-vis). The Ba0.5Rb0.5LaTeO6 and Ba0.5Rb0.5La0.9Sm0.1TeO6 was assumed to be indirect band gap and the optical band gap obtained for Ba0.5Rb0.5LaTeO6 and Ba0.5Rb0.5La0.9Sm0.1TeO6 were 4.1 eV and 4.3 eV respectively