In this study, we investigated the gelation kinetics of gold nanowires (AuNWs) to understand its mechanisms. Gelation was induced by the addition of triphenylphosphine (PPh₃), which replaces oleylamine (OAm) as ligands on the wire surfaces. This leads to the formation of a gel body that shrank over time and adopted the shape of the vessel. In-situ transmission electron microcopy (TEM) showed that the wires bundled and formed an entangled network. Bundle sizes and the degree of wire entanglement both increased with gelation time. Small-angle X-ray scattering (SAXS) had a pronounced structure factor peak that we used to quantify the changes in bundling of the nanowires. Over time, the peak broadened, which confirms the decreasing size of bundles of nanowires observed by TEM. Rheological measurements of the mechanical network indicated elastic behavior of the AuNW gels in the linear viscoelastic range (LVE) range that is characterized by higher values for the storage modulus G’ than the loss modulus G’’. Previously described AuNW gels in literature did not exhibit elastic behavior under applied shear stress. This difference may be to the exchange of OAm by PPh₃ on the wire surfaces that leads to stronger interactions between the wires and possibly to π-π stacking. Increased microscopic attraction may lead to the elastic behavior as shown by LVE range. We performed additional rheological studies at different molar ratios between Gold and PPh₃ during the preparation of the AuNW gels. The results show that G’ and thus elasticity increased with increasing excess of PPh₃ until a certain critical molar ratio. We hypothesize that a higher excess of PPh₃ replaces more OAm on the surfaces, which leads to stronger wire-wire interactions and, therefore, higher structural stability.