The study provides a unique approach for controlling the structural, electrical, optical, and photoluminescence characteristics of oxostannate Cs2Sn2O3 (C2T2O3) nanostructures through the process of co-precipitation. XRD, XPS, Raman, HRTEM, and FESEM techniques were employed to investigate and describe the impact of varying annealing temperatures on a specific system. The diffraction patterns indicate the existence of an orthorhombic oxostannate C2T2O3 phase, wherein as the temperature rises, the size of the crystallites grows. Additionally, it is important to acknowledge that the spectra of Cs 3d, Sn 3d, and O 1s demonstrate the formation of materials without alteration in the position of their primary peaks when exposed to variations in temperature. Under the influence of annealing temperature, the real components of permittivity and electrical conductivity demonstrate superior characteristics in terms of frequency dependence. The optical band gap for the as-prepared C2T2O3 decreased with annealing at temperatures of 600 °C and 900 °C to 3.8 eV and 3.7 eV, respectively. The photoluminescence (PL) emission bands’ positions and intensities demonstrate a significant level of sensitivity towards the existence of interstitial Cs-Sn defects. The electrical performance and luminescence emissions of nanostructured C2T2O3 systems are promising, offering a wide range of sensitivity for energy storage, optoelectronics, and luminescence applications.