The growth mechanism of silver nanowires (AgNWs) in solution has been thoroughly investigated and it has been demonstrated that factors like oxidative etching and inclusion of Cl- ions in the reaction system play critical roles in the formation of AgNWs. This research is the first to report the growth mechanism of AgNWs in the solid state on a chitosan polymer film with respect to factors such as oxidative etching, Cl- ions and time. The AgNW synthetic method is a green process that involves aqueous solvents for film preparation and ambient conditions for AgNW growth. It is demonstrated that the source of the silver precursor for this solid state AgNW growth is the cuboidal AgCl nanoparticles that form during the solution preparation. Furthermore, it is shown that the 〈111〉 crystal faces of these cuboidal AgCl nanoparticles are the nucleation sites of AgNW growth. Unlike solution-based AgNW synthetic processes, the AgNWs generated by the chitosan film-based method are irregular and present lateral as well as longitudinal growth, which suggests a slightly different mechanism from the solution-based AgNW growth.