Gold nanowires with a mean diameter of 1.7 nm were synthesized by reduction of HAuCl4 in a solution of oleylamine (OY) in hexane. A bilayer of oleylammonium chloride/oleylamine at the surface of the raw nanowires was evidenced by NMR and diffusion ordered spectroscopy (DOSY) experiments. After washing a monolayer of oleylammonium chloride remained at the surface of the nanowires. The oleylammonium chloride layer could be progressively replaced by a phosphine shell as evidenced with NMR and DOSY experiments, which are in good agreement with the adsorption energies given by density functional theory calculations. The nanowires crystallize into hexagonal superlattices with a lattice parameter that can be tailored depending on the ligand shell. Small-angle X-ray scattering showed the following lattice parameters: Au@OY+Cl-(OY) (a = 7.2 nm) > Au@TOPO/OY (a = 6.6 nm) > Au@ OY+Cl- (a = 4.1 nm) > Au@TOP (a = 3.75 nm). This is one of a few examples of surface modification of ultrathin nanowires that does not alter their morphology. Moreover, the nanowires coated with phosphines exhibited long time stability (at the opposite of other ligands like thiols) opening the way to more complex functionalization.