"Surface-programmed assembly" is presented as a technique (see Figure) to achieve high-precision assembly and alignment of a large number of pristine V2O5 nanowires on solid substrates. Positively charged surface molecular patterns guide the assembly and alignment of negatively charged V2O5 nanowires on solid substrates. Large-scale assembly Of V2O5 nanowire-based transistors is demonstrated and their gating effects are confirmed.