In this study, bilayer Ti/Mg thin films were deposited onto plain as well ITO coated glass substrates using the r.f. magnetron sputtering deposition technique. The prepared thin films were annealed at 423 K to facilitate mixing at the Ti/Mg interface. Structural properties were analyzed through X-ray diffraction (XRD), while surface morphology was assessed using field emission scanning electron microscopy (FESEM) coupled with energy dispersive spectroscopy (EDS). FESEM images revealed a uniform film deposition, and EDS confirmed the elemental composition of the films. Optical and electrical characteristics were examined using UV-Vis spectroscopy, a Keithley electrometer, and Hall Effect measurement setups. The optical band gap of the as-deposited films was determined to be 3.83 eV, which increased to 4.09 eV after annealing. Additionally, annealing resulted in a significant decrease in conductivity from 8.51 × 103 Ω−1 cm−1 to 0.02 × 103 Ω−1 cm−1. Hall Effect measurements and I-V characteristics confirmed the n-type semiconducting nature of the prepared thin films. The results suggest that these thin film materials could have potential applications in smart windows and hydrogen sensors.