The development of a method for large-scale printing of nanowire (NW) arrays onto a desired substrate is crucial for fabricating high-performance NW-based electronics. Here, the alignment of highly ordered and dense silicon (Si) NW arrays at anisotropically etched micro-engraved structures is demonstrated using a simple evaporation process. During evaporation, entropic attraction combined with the internal flow of the NW solution induced the alignment of NWs at the corners of pre-defined structures, and the assembly characteristics of the NWs were highly dependent on the polarity of the NW solutions. After complete evaporation, the aligned NW arrays are subsequently transferred onto a flexible substrate with 95% selectivity using a direct gravure printing technique. As a proof-of-concept, flexible back-gated NW field-effect transistors (FETs) are fabricated. The fabricated FETs have an effective hole mobility of 17.1 cm2·V−1·s−1 and an on/off ratio of ∼2.6 × 105.