The growth of benzotriazole (BTAH) via solution deposition onto copper monolayers prepared via underpotential deposition (UPD) on Au(111)/mica substrates has been investigated using X-ray photoelectron spectroscopy (XPS) and ambient scanning tunnelling microscopy (STM) as a function of solution pH and immersion time. Adsorbed species have been found sensitive to the solution pH with a higher benzotriazole surface concentration following deposition from an acidic environment. Although the layers prepared at different pH are chemically different, as highlighted by XPS, similar morphologies are recorded via STM. These results are critically discussed in the light of some of the adsorption models previously reported.