Since the discovery of desorption ionization on porous silicon (DIOS), intact laser desorption ionization (LDI) of thermally labile molecules from nanostructured surfaces has been the subject of extensive investigations. 1,2 In fact, early studies focused on the ionization of small molecules because the use of excess matrices in MALDI (matrix-assisted LDI) has certain limitations in the low-mass region (m/z < 400), including matrix peak interference. However, with recent advances in nanostructure fabrication, a variety of surface nanostructures and materials have been examined and some of them exhibited their LDI capability extending beyond the smallmolecule regime. Now a possible realization of matrix-free LDI as a true alternative to conventional MALDI for protein mass spectrometry can be anticipated.Although the mechanism of LDI on the surface of nanostructures is too complex to understand fully, some previous studies showed that intact desorption might be promoted by rapid surface heating caused by momentary trapping of absorbed laser energy within the nanostructures before it dissipates into the bulk substrates. 3-5 For example, LDI can cause a rapid increase in surface temperature to 1000 K or more, in a 10-ns time scale for Si surface nanostructures.Among the many surface materials that might enhance LDI, we chose metal oxide nanowires in this study. The high melting points of metal oxides may offer robust structures against laser ablation for this application. In addition, reproducible fabrication of nanostructures by using metal oxides is well known. However, investigations of LDI from metal oxides are rare. A few studies on zinc oxide (ZnO) nanowires revealed limited LDI performance for small drug molecules. But LDI of large molecules, such as peptides, were not successful at all from the ZnO nanostructured surfaces. 4,6 Herein, we report the observation of pronounced LDI of peptide molecules from the arrays of tungsten oxide (WO 3 ) nanowires, which possess promising material properties for the LDI mechanism based on rapid surface heating. WO 3 is a semiconductor (bandgap~2.73 eV) with a high melting point (1473 C), which is suitable for high-power UV laser irradiation. Its very low thermal conductivity of 1.63 W m −1 K −1 may promote the rapid surface heating required for intact desorption of thermally labile molecules, which is much lower than for Si (150 W m −1 K −1 ) and smaller still than for amorphous Si (5.5 W m −1 K −1 ). 5 Although ZnO nanowires were not successful for LDI of peptides, 4,6 a few previous studies including LDI using WO 3 nanoparticles as a matrix alternative 7 and LDI from rough WO 3 surfaces with micrometer dimensions suggest that WO 3 is a promising material for LDI surfaces. 8 For this study, length-controlled WO 3 surface nanowires with a 50 nm diameter were prepared by utilizing anodic Al 2 O 3 templates. Careful control of the fabrication process yielded a set of length-controlled nanowire arrays (Figure 1). The lengths of the nanowires covered a range of 60-250 nm. Typic...