This communication reports the synthesis of Sn1-xCexO2 (0 ≤ x ≤ 1) nanocomposites produced by cost effective and viable sol-gel route followed by spin coating technique. As prepared nano powders/thin films were annealed at 950 °C for 3 h. Complimentary characterization tools like XRD, FTIR, Raman, UV–visible, PL spectroscopies and simultaneous thermal analyzer were employed to determine structural, optical and thermal parameters of prepared powdered samples/thin films with different compositions. The results indicated that annealed samples contained tetragonal SnO2 and cubic CeO2 phases. Profile R-parameters were determined from Rietveld refinenment. Alteration of crystallite size, lattice constants, microstrain, dislocation density and lattice expansion with composition has been studied. The complex dielectric constant, extinction coefficient, refractive index have been analyzed through optical absorption spectroscopy. The energy band gap has been tuned with composition in the range of 3.19–3.88 eV. Different thermodynamic parameters like enthalpy, activation energy, entropy and Gibbs free energy have been estimated from thermal analysis. TGA/DTA/DTG thermograms showed an exothermic peak correlated to a weight loss resulting from the combustion of organic residues due to crystallization.