Highly transparent indium-free multilayers of TiO2/Cu/TiO2 were obtained by means of annealing. The effects of Cu thickness and annealing temperature on the electrical and optical properties were investigated. The critical thickness of Cu mid-layer with optimal electrical and optical properties was 10 nm, with the figure of merit reaching as high as 5 × 10−3 Ω−1. Partial crystallization of the TiO2 layer enhanced the electrical and optical properties upon annealing. Electrothermal experiments showed that temperatures of more than 100 °C can be reached at a heating rate of 2 °C/s without any damage to the multilayers. The experimental results indicate that reliable transparent TiO2/Cu/TiO2 multilayers can be used for electrothermal application.