We investigated the ordering of gold nanowires that settled from aqueous suspension onto a glass substrate due to gravity. The nanowires, ca. 300 nm in cross-sectional diameter and ca. 2, 4, or 7 microns in length, were coated with 2-mercaptoethanesulfonic acid to provide electrostatic repulsion and prevent aggregation. The layer of nanowires in direct contact with the substrate was examined from below using optical microscopy and found to exhibit smectic-like ordering. The extent of smectic ordering depended on nanowire length with the shortest (2 μm) nanowires exhibiting the best ordering. To understand the assembly in this system, we used canonical Monte Carlo simulations to model the two-dimensional ordering of the nanowires on a substrate. We accounted for van der Waals and electrostatic interactions between the nanowires. The simulations reproduced the experimental trends and showed that roughness at the ends of the nanowires, which locally increased electrostatic repulsion, is critical to correctly predicting the experimentally observed smectic ordering.