Self-assembled monolayers (SAM) and multilayers of organic materials have been intensely studied in the past years, due to their numerous potential applications as, for example, lubricants, corrosioninhibitors and/or adhesion-promoters [1,2]. In this talk, we will present results of several studies carried out using Atomic Force Microscopy to investigate octadecylphosphonic acid (OPA) SAM deposited on mica. We have assessed various mechanisms of assembling, disassembling and reassembling the SAM on mica. The SAM deposition method employed in this work was drip coating using an OPA solution. We have used two different solvents, which exhibit very different OPA solubility, in this work: ethanol and trihydrofuran (THF). Regarding the assembling studies, we will show the formation of groups of OPA double-layers as the initial deposition stage (deposition time < 2 seconds) when using ethanol-based solutions. We will also show that annealing such samples at 60°C produces, favorably, OPA quadruple-layers, as shown in figures la and lb, respectively.