In the last few years, the development of versatile coating chemistries has become a hot topic in surface science after the discovery that catecholamines can lead to conformal coatings upon oxidation from aqueous solutions. Recently, it was found that aminomalononitrile (AMN), a molecule implicated in the appearance of life on earth, is an excellent prototype of novel material-independent surface functionalizing agents leading to conformal and biocompatible coatings in a simple and direct chemical process from aqueous solutions. So far, very little insight has been gained regarding the mechanisms underlying coating deposition. In this paper, we show that the chemical evolution of AMN film deposition under slightly basic conditions is different in solution and on silica. Thereon, the coating proceeds via a nucleation process followed by further deposition of islands which evolve to produce nitrogen-rich superhydrophilic fibrillar structures. Additionally, we show that AMN-based material can form films at the air-solution interface from unshaken solutions. These results open new vistas into the chemistry of HCN-derived species of potential relevance in materials science.