HfO₂ and V₂O₅ as multi-layer thin films are discussed for their potential use as transparent heat mirrors. Multi-layered HfO₂/V₂O₅/HfO₂ thin films with a thickness of 100/60/100 nm were prepared via e-beam evaporation on a soda–lime glass substrate. Rutherford backscattering confirmed the multi-layer structure with uniform surface. The as-deposited thin films were annealed at 300 °C and 400 °C, respectively, for 1 h in air. The transmittance of approximately 90% was obtained for all thin films. Due to the relatively low thickness and non-stoichiometry of HfO₂, a band gap of approximately 3.25 eV was determined (instead of the theoretical 5.3–5.7 eV). The as-deposited thin films possessed conductivity of approximately 0.2 Ω⁻¹cm⁻¹ and increased to 1 Ω⁻¹cm⁻¹ and 2 Ω⁻¹cm⁻¹ for thin films annealed at 300 and 400 °C, respectively. Due to the unique intrinsic properties of HfO₂/V₂O₅/HfO₂ thin films, the results obtained are promising for application as a transparent heat mirror.