Ultrafine one-dimensional (1-D) semiconducting nanostructures with diameters below 10 nm are attracting great research attention. Using a laser-ablation chemical vapour deposition (CVD) method, we reported the synthesis of single-crystal In2O3 nanowires with diameter below 4 nm. The as-synthesized ultrathin In2O3 nanowires act as the ultrathin branches of hierarchical In2O3 nanostructures and show fast photoinduced switching surface wettability behaviors and the contact angle decreased from 134.3o to 0o in 10 min. Transparent thin-film transistors (TTFTs) were fabricated using the as-synthesized product and the device conductance was 1-2 orders higher than the average conductance of the In2O3 single nanowire devices, revealing good opportunity in transparent electronics.